Aryl compounds and polymers and methods of making and using the same

ABSTRACT

Disclosed herein are embodiments of aryl compounds and polymers thereof that are made using methods that do not require harsh conditions or expensive reagents. The methods disclosed herein utilize precursor compounds that can be polymerized to form polycyclic aromatic hydrocarbons and polymers, such as carbon-based polymers like nanostructures (e.g., graphene or graphene-like nanoribbons).

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.15/558,978, filed on Sep. 15, 2017, which is the U.S. National Stage ofInternational Application No. PCT/US2016/023179, filed Mar. 18, 2016,which was published in English under PCT Article 21(2), which claims thebenefit of, and priority to, the earlier filing date of U.S. ProvisionalPatent Application No. 62/135,692, filed on Mar. 19, 2015, and U.S.Provisional Patent Application No. 62/182,351, filed on Jun. 19, 2015;each of these prior applications is herein incorporated by reference inits entirety.

FIELD

The present disclosure concerns aryl compounds and polymeric arylcompounds and methods of making and using the same.

BACKGROUND

Peropyrene compounds, as large polycyclic aromatic hydrocarbons (LPAH),comprise structural features that convey unique photophysical propertiesto such compounds. However, due to difficult preparation andderivatization of such compounds, their utility has yet to be utilizedin various applications. Perylenediimide derivatives, which comprise asimilar core as peropyrene compounds, have been prepared and analyzed.Chiral conjugated molecules are a class of interesting research as thesemolecules have utility in areas such as polarized photoluminescence,enantioselective sensing, etc. Methods exist to introduce chirality intoconjugated materials, including appending a chiral auxiliary, orsynthesizing an LPAH that is twisted giving rise to axial chirality,such as seen in helicenes. For example, axial chirality in twistedperylenediimide derivatives has been observed where substituents on thecove positions cause twisting of the PAH to relieve steric strain. Thisis seen even if the substituent is a hydrogen, albeit, with a lowbarrier to inversion of enantiomers. There is a need in the art,however, for methods to introduce chirality into peropyrene molecules.

Other aromatic ring systems comprising peropyrene cores also are ofinterest, such as graphene, an organic material comprised of a2-dimensional monolayer of sp2-hybridized carbon atoms. Graphene hasbeen shown to have interesting electronic, thermal, mechanical, andoptical properties. The properties of graphene materials can be alteredby varying the size and shape of the graphene sheets. These materialsare of interest for device applications such as thin-film transistors(TFTs) and field-effect transistors (FETs) due to their interestingelectronic properties. Specifically, graphene is a zero band-gapsemiconductor whereas graphene nanoribbons have a persistent band-gapmaking them useful material in thin-film transistors (TFTs). Oneparticular area of interest is the scission of graphene sheets into thinstrips known as graphene nanoribbons that have different properties thangraphene. The approach of exfoliation of graphite to produce graphene,followed by scission of graphene is known as a “top-down” approach.These methods result in mixtures of different sizes and shapes ofgraphene nanoribbons and the products typically have poor solubility,making processing of the material for device applications difficult.Also, the harsh conditions used to produce graphene nanoribbons using a“top-down” approach (lithographic patterning of graphene or unzipping ofcarbon nanotubes) can result in oxidized graphene nanoribbons, whichsignificantly affects the electronic properties of the material. Thus,there is a need in the art for methods of making graphene nanoribbonsthat can address these drawbacks.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a peropyrene core (100), a chiral peropyrene core(102) and top (104 and 106, respectively) and side views (108 and 110,respectively) of these cores.

FIG. 2 is a rotating frame Overhauser effect spectrum (ROESY spectrum)of a representative intermediate compound disclosed herein.

FIG. 3 is a NOESY spectrum of a representative intermediate compounddisclosed herein.

FIG. 4 is a combined UV-Vis spectrum and fluorescence spectrum ofrepresentative intermediates and compounds disclosed herein.

FIG. 5 is a combined UV-Vis spectrum and fluorescence spectrum ofrepresentative intermediates and compounds disclosed herein.

FIG. 6 is a combined HPLC trace of representative intermediatesdisclosed herein.

FIG. 7 is a Merck Molecular Force Field 94 calculation image ofrepresentative compounds disclosed herein.

FIG. 8 illustrates representative intermediate compounds disclosedherein.

FIG. 9 is a combined UV-Vis and fluorescence spectrum of representativecompounds disclosed herein.

FIGS. 10A and 10B are ¹H-NMR (FIG. 10A) and ¹³C-NMR (FIG. 10B) spectraof a representative intermediate compound disclosed herein.

FIGS. 11A and 11B are ¹H-NMR (FIG. 11A) and ¹³C-NMR (FIG. 11B) spectraof a representative intermediate compound disclosed herein.

FIGS. 12A and 12B are ¹H-NMR (FIG. 12A) and ¹³C-NMR (FIG. 12B) spectraof a representative intermediate compound disclosed herein.

FIGS. 13A and 13B are ¹H-NMR (FIG. 13A) and ¹³C-NMR (FIG. 13B) spectraof a representative boronic ester compound disclosed herein.

FIGS. 14A and 14B are ¹H-NMR (FIG. 14A) and ¹³C-NMR (FIG. 14B) spectraof a representative boronic ester compound disclosed herein.

FIGS. 15A and 15B are ¹H-NMR (FIG. 15A) and ¹³C-NMR (FIG. 15B) spectraof a representative boronic ester compound disclosed herein.

FIGS. 16A and 16B are ¹H-NMR (FIG. 16A) and ¹³C-NMR (FIG. 16B) spectraof a representative peropyrene precursor compound disclosed herein.

FIGS. 17A and 17B are ¹H-NMR (FIG. 17A) and ¹³C-NMR (FIG. 17B) spectraof a representative peropyrene compound disclosed herein.

FIGS. 18A and 18B are ¹H-NMR (FIG. 18A) and ¹³C-NMR (FIG. 18B) spectraof a representative peropyrene precursor compound disclosed herein.

FIGS. 19A and 19B are ¹H-NMR (FIG. 19A) and ¹³C-NMR (FIG. 19B) spectraof a representative intermediate compound disclosed herein.

FIGS. 20A and 20B are ¹H-NMR (FIG. 20A) and ¹³C-NMR (FIG. 20B) spectraof a representative intermediate compound disclosed herein.

FIGS. 21A and 21B are ¹H-NMR (FIG. 21A) and ¹³C-NMR (FIG. 21B) spectraof a representative intermediate compound disclosed herein.

FIGS. 22A and 22B are ¹H-NMR (FIG. 22A) and ¹³C-NMR (FIG. 22B) spectraof a representative chiral peropyrene compound disclosed herein.

FIGS. 23A and 23B are ¹H-NMR (FIG. 23A) and ¹³C-NMR (FIG. 23B) spectraof a representative chiral peropyrene compound disclosed herein.

FIGS. 24A and 24B are ¹H-NMR (FIG. 24A) and ¹³C-NMR (FIG. 24B) spectraof a representative chiral peropyrene compound disclosed herein.

FIG. 25 is a gel permeation chromatogram of an exemplary compoundembodiment.

FIG. 26 is a combined Raman spectrum illustrating spectra of anexemplary compound embodiment, the compound after baseline correction,and a baseline spectrum.

FIG. 27 is a combined Raman spectrum illustrating spectra of anexemplary compound embodiment, the compound after baseline correction,and a baseline spectrum.

FIG. 28 is a combined UV-Vis spectrum illustrating spectra of anexemplary peropyrene polymer and a polymer synthesized using variousdifferent acids disclosed herein.

FIGS. 29A and 29B are ¹H-NMR (FIG. 29A) and ¹³C-NMR (FIG. 29B) spectraof a representative intermediate compound used in methods disclosedherein.

FIGS. 30A and 30B are ¹H-NMR (FIG. 30A) and ¹³C-NMR (FIG. 30B) spectraof a representative intermediate compound used in methods disclosedherein.

FIGS. 31A and 31B are ¹H-NMR (FIG. 31A) and ¹³C-NMR (FIG. 31B) spectraof a representative intermediate compound used in methods disclosedherein.

FIGS. 32A and 32B are H-NMR (FIG. 32A) and ¹³C-NMR (FIG. 32B) spectra ofa representative intermediate compound used in methods disclosed herein.

FIGS. 33A and 33B are H-NMR (FIG. 33A) and ¹³C-NMR (FIG. 33B) spectra ofa representative boronic ester compound used in methods disclosedherein.

FIGS. 34A and 34B are ¹H-NMR (FIG. 34A) and ¹³C-NMR (FIG. 34B) spectraof a representative polymer precursor used in methods disclosed herein.

FIG. 35 is a combined H-NMR spectrum illustrating results from ¹H-NMRanalysis of an intermediate embodiment, a pyrene embodiment, a polymerembodiment, and a polymer embodiment.

FIG. 36 is a combined ¹³C-NMR spectrum illustrating results from ¹³C-NMRanalysis of the intermediate embodiment, pyrene embodiment, polymerembodiment, and polymer embodiment of FIG. 35.

FIG. 37 is a combined FTIR full spectrum illustrating spectra obtainedfrom IR analysis of a polymer embodiment and a polymer embodiment formedusing methyl sulfonic acid (MSA).

FIG. 38 is a combined FTIR full spectrum illustrating spectra obtainedfrom IR analysis of a polymer embodiment and a polymer embodiment formedusing TFA-TfOH.

FIGS. 39A-39G are images of polymer embodiments; FIG. 39A is a TEM imageof a polymer embodiment; FIG. 39B is a TEM image using RuO₄ stainingthat shows curved regions of a polymer embodiment; FIG. 39C is a zoomedTEM image of a polymer sheet illustrating long linear strands ofnanoribbons aggregated together; FIG. 39D is an XRD image of a polymerembodiment illustrating the crystallinity of a polymer embodiment; FIG.39E is a high resolution TEM image of a polymer embodiment on a coppergrid coated with lacey carbon;

FIG. 39F is a TEM image obtained using RuO₄ staining for high contrastand illustrating a thin sheet of aggregated nanoribbons; and FIG. 39G isa TEM image showing a bundle of short nanoribbons that are approximately30 nm in length.

FIG. 40 provides exemplary STM and space-filled images of exemplarynanostructured compounds.

FIG. 41 is a combined ¹H-NMR spectrum of pyrene intermediates andcompounds disclosed herein.

FIG. 42 is a combined ¹H-NMR spectrum of polymer and polymer productsdisclosed herein.

FIG. 43 is a combined ¹H-NMR spectrum of polymer and polymer productsdisclosed herein.

FIG. 44 is a combined ¹H-NMR spectrum of a representative polymer and arepresentative polymer product disclosed herein.

FIG. 45 is a combined IR spectrum of polymer and polymer productsdisclosed herein.

FIG. 46 shows STM images of compounds disclosed herein.

FIG. 47 is an image illustrating the twisting characteristics ofnanostructured compounds disclosed herein.

FIGS. 48A and 48B are combined ¹H-NMR spectra of compounds disclosedherein.

FIGS. 49A and 49B are spectra obtained from representative compoundsdisclosed herein; FIG. 49A is a combined normalized UV-vis absorptionspectrum and FIG. 49B is a combined normalized fluorescence emissionspectrum.

FIGS. 50A and 50B are STM images of a representative compound at theHOPG/TCB interface wherein I=0.4 nA, V=300 mV (FIG. 50A) and I=0.3 nA,V=250 mV (FIG. 50B).

FIG. 51 is an X-ray image of a representative compound.

FIG. 52 is an X-ray image of a representative compound.

FIG. 53 is an X-ray image of a representative compound.

FIG. 54 is an X-ray image of a representative compound.

DETAILED DESCRIPTION I. Explanation of Terms

The following explanations of terms are provided to better describe thepresent disclosure and to guide those of ordinary skill in the art inthe practice of the present disclosure. As used herein, “comprising”means “including” and the singular forms “a” or “an” or “the” includeplural references unless the context clearly dictates otherwise. Theterm “or” refers to a single element of stated alternative elements or acombination of two or more elements, unless the context clearlyindicates otherwise.

Although the steps of some of the disclosed methods are described in aparticular, sequential order for convenient presentation, it should beunderstood that this manner of description encompasses rearrangement,unless a particular ordering is required by specific language set forthbelow. For example, steps described sequentially may in some cases berearranged or performed concurrently. Additionally, the descriptionsometimes uses terms like “produce” and “provide” to describe thedisclosed methods. These terms are high-level abstractions of the actualsteps that are performed. The actual steps that correspond to theseterms will vary depending on the particular implementation and arereadily discernible by one of ordinary skill in the art.

Unless explained otherwise, all technical and scientific terms usedherein have the same meaning as commonly understood to one of ordinaryskill in the art to which this disclosure belongs. Although methods andcompounds similar or equivalent to those described herein can be used inthe practice or testing of the present disclosure, suitable methods andcompounds are described below. The compounds, methods, and examples areillustrative only and not intended to be limiting, unless otherwiseindicated. Other features of the disclosure are apparent from thefollowing detailed description and the claims.

Unless otherwise indicated, all numbers expressing quantities ofcomponents, molecular weights, percentages, temperatures, times, and soforth, as used in the specification or claims are to be understood asbeing modified by the term “about.” Accordingly, unless otherwiseindicated, implicitly or explicitly, the numerical parameters set forthare approximations that can depend on the desired properties soughtand/or limits of detection under standard test conditions/methods. Whendirectly and explicitly distinguishing embodiments from discussed priorart, the embodiment numbers are not approximates unless the word “about”is recited.

Furthermore, not all alternatives recited herein are equivalents. Thefollowing terms and definitions are provided. Certain functional groupterms include an R^(a) group that, though not part of the definedfunctional group, indicates how the functional group attaches to thecompound to which it is bound.

Aliphatic: A hydrocarbon, or a radical thereof, having at least onecarbon atom to 50 carbon atoms, such as one to 25 carbon atoms, or oneto ten carbon atoms, and which includes alkanes (or alkyl), alkenes (oralkenyl), alkynes (or alkynyl), including cyclic versions thereof, andfurther including straight- and branched-chain arrangements, and allstereo and position isomers as well.

Alkyl: A saturated monovalent hydrocarbon having at least one carbonatom to 50 carbon atoms, such as one to 25 carbon atoms, or one to tencarbon atoms, wherein the saturated monovalent hydrocarbon can bederived from removing one hydrogen atom from one carbon atom of a parentcompound (e.g., alkane). An alkyl group can be branched, straight-chain,or cyclic (e.g., cycloalkyl).

Alkenyl: An unsaturated monovalent hydrocarbon having at least twocarbon atoms 50 carbon atoms, such as two to 25 carbon atoms, or two toten carbon atoms, and at least one carbon-carbon double bond, whereinthe unsaturated monovalent hydrocarbon can be derived from removing onehydrogen atom from one carbon atom of a parent alkene. An alkenyl groupcan be branched, straight-chain, cyclic (e.g., cylcoalkenyl), cis, ortrans (e.g., E or Z).

Alkynyl: An unsaturated monovalent hydrocarbon having at least twocarbon atoms 50 carbon atoms, such as two to 25 carbon atoms, or two toten carbon atoms and at least one carbon-carbon triple bond, wherein theunsaturated monovalent hydrocarbon can be derived from removing onehydrogen atom from one carbon atom of a parent alkyne. An alkynyl groupcan be branched, straight-chain, or cyclic (e.g., cycloalkynyl).

Alkoxy: —O-alkyl, —O-alkenyl, or —O-alkynyl, with exemplary embodimentsincluding, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, t-butoxy, sec-butoxy, n-pentoxy.

Ambient Temperature: A temperature ranging from 16° C. to 26° C., suchas 19° C. to 25° C., or 20° C. to 25° C.

Amine: —NR^(b)R^(c), wherein each of R^(b) and R^(c) independently isselected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl,heteroalkenyl, heteroalkynyl, heteroaryl, and any combination thereof.

Aryl: An aromatic carbocyclic group comprising at least five carbonatoms to 15 carbon atoms, such as five to ten carbon atoms, having asingle ring or multiple condensed rings, which condensed rings can ormay not be aromatic provided that the point of attachment is through anatom of the aromatic carbocyclic group.

Diyne: An aryl compound comprising two alkyne groups, typically whereinthe alkyne groups are positioned on the aryl ring such that there is atleast one carbon atom of the aryl compound located between the twoalkyne groups.

Electron-Accepting Group: A functional group capable of acceptingelectron density from the ring to which it is directly attached, such asby inductive electron withdrawal.

Electron-Donating Group: A functional group capable of donating at leasta portion of its electron density into the ring to which it is directlyattached, such as by resonance.

Haloaliphatic: An aliphatic group wherein one or more hydrogen atoms,such as one to 10 hydrogen atoms, independently is replaced with ahalogen atom, such as fluoro, bromo, chloro, or iodo.

Haloalkyl: An alkyl group wherein one or more hydrogen atoms, such asone to 10 hydrogen atoms, independently is replaced with a halogen atom,such as fluoro, bromo, chloro, or iodo. In an independent embodiment,haloalkyl can be a CX₃ group, wherein each X independently can beselected from fluoro, bromo, chloro, or iodo.

Halogen-Metal Exchange: A reaction wherein a bond between a halogen atomand a carbon atom is converted into a bond between a metal atom and thecarbon atom using a metal-containing compound as described herein.

Heteroaliphatic: An aliphatic group comprising at least one heteroatomto 20 heteroatoms, such as one to 15 heteroatoms, or one to 5heteroatoms, which can be selected from, but not limited to oxygen,nitrogen, sulfur, selenium, phosphorous, and oxidized forms thereofwithin the group.

Heteroalkyl/Heteroalkenyl/Heteroalkynyl: An alkyl, alkenyl, or alkynylgroup (which can be branched, straight-chain, or cyclic) comprising atleast one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms,or one to 5 heteroatoms, which can be selected from, but not limited tooxygen, nitrogen, sulfur, selenium, phosphorous, and oxidized formsthereof within the group.

Heteroaryl: An aryl group comprising at least one heteroatom to sixheteroatoms, such as one to four heteroatoms, which can be selectedfrom, but not limited to oxygen, nitrogen, sulfur, selenium,phosphorous, and oxidized forms thereof within the ring. Such heteroarylgroups can have a single ring or multiple condensed rings, wherein thecondensed rings may or may not be aromatic and/or contain a heteroatom,provided that the point of attachment is through an atom of the aromaticheteroaryl group.

Metal-Containing Compound: A metal-containing compound can be anycompound comprising a metal and that is capable of undergoing ahalogen-metal exchange reaction with a compound or compound precursordisclosed herein. Suitable metal-containing compounds include, but arenot limited to, Mg, Li, and the like.

A person of ordinary skill in the art would recognize that thedefinitions provided above are not intended to include impermissiblesubstitution patterns (e.g., methyl substituted with 5 different groups,and the like). Such impermissible substitution patterns are easilyrecognized by a person of ordinary skill in the art. Any functionalgroup disclosed herein and/or defined above can be substituted orunsubstituted, unless otherwise indicated herein.

II. Introduction

Methods disclosed herein address the short-comings of conventionalmethods for making benzene-containing compounds, such as pyrenecompounds, peropyrene-based compounds, and polymeric structures, such asnanostructures (e.g., nanoribbons). In particular, a high yieldingalkyne benzannulation method is used that provides polycyclic aromatichydrocarbons (PAHs) such as pyrenes and peropyrenes. In contrast toconventional peropyrene synthesis, the methods disclosed herein areefficient, high-yielding, and do not require harsh reaction conditions.In some embodiments, 4,10-disubstituted pyrene derivatives can beprepared using an efficient Brønsted acid catalyzed double cyclizationof 2,6-dialkynylbiphenyl derivatives. Exemplary peropyrenes areillustrated in FIG. 1, which provides different view of the compounds.

Since the discovery of graphene, research has been done on relatedmaterials, namely, graphene nanoribbons. The harsh conditions used toproduce graphene nanoribbons using a “top-down” approach (lithographicpatterning of graphene or unzipping of carbon nanotubes) can result inoxidized graphene nanoribbons, which significantly affects theelectronic properties of the material. Also, these top-down methodscommonly produce impure graphene nanoribbons as a mixture of differentsizes and shapes with poor solubility, which complicates processing ofthe materials for device applications. In other conventional methods,solution-mediated or surface-assisted polymerization of molecularprecursors into linear polyphenylenes followed by their subsequentcyclodehydrogenation can be used to generate nanoribbons. Some“bottom-up” approaches towards graphene nanoribbons have been reported,which rely on oxidative aryl-aryl bond formation (e.g., the Schollreaction) for key C—C bond forming reactions; however, the harshconditions required for these methods significantly limit thefunctionality that can be incorporated into the graphene nanoribbons andthus limit the ability to tune the properties via substitution. Also,only limited quantities of material can be produced with conventionalbottom-up methods.

In some embodiments, twisted and axially chiral peropyrene derivativescan be made using the methods disclosed herein. These methods also canbe modified to make narrow polymeric nanostructures, such as nanoribbons(ca. 0.5 nm wide) that are highly soluble in a number of common organicsolvents. The methods disclosed herein allow for better control of thesize, shape, and functionalization of the nanostructures (e.g.,nanoribbons), leading to improved solubility and material properties. Inembodiments disclosed herein, highly soluble and very narrow armchairedge polymeric structures (e.g., nanoribbons) can be made using analkyne benzannulation strategy caused by Brønsted acid, which does notrequire a cyclodehydrogenation reaction step. These soluble and narrowpolymeric structures may have significant value in many nano-basedsemiconductor applications (e.g., FET applications) in view of theirmetallic to semiconducting properties. In some embodiments, thepolymeric compounds (e.g., nanoribbons, such as graphene nanoribbons)are characterized by gel permeation chromatography (GPC) (e.g., FIG.25), high performance liquid chromatography (HPLC) (e.g., FIG. 6),nuclear magnetic resonance (NMR), infrared spectroscopy (e.g., FIGS. 37and 38), Raman spectroscopy (e.g., FIGS. 26 and 27), andultraviolet-visible (UV-vis) and fluorescence spectroscopy (e.g., FIGS.4, 5, 9, 49A and 49B), as well as transmission electron microscopy (TEM)(e.g., FIGS. 39A-39G), and scanning tunneling microscopy (STM) (e.g.,FIG. 40 and FIGS. 50A and 50B).

III. Compounds

In particular disclosed embodiments, compounds having the followingformulas can be made according to the methods disclosed herein.

With reference to Formulas 1-5, each R¹ moiety can be chosen to promotesolubility and/or to control the chemical and/or electrochemicalproperties of the compound. In some embodiments, each R¹ independentlycan be selected from hydrogen, aliphatic, aryl, heteroaliphatic, orheteroaryl; each R^(a) independently can be selected from aryl; arylsubstituted with one or more functional groups selected from aliphatic,alkoxy, amide, amine, thioether, haloalkyl, nitro, halo, silyl,cycloaliphatic, aryl, and the like; or an electron-donating group; eachn independently can be 1, 2, or 3; and m can be 0 to 1000, or higher.Exemplary electron-donating groups include, but are not limited to,alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, silyloxy,heteroaryl (e.g., thiophene), and the like. Aryl rings substituted withone or more functional groups can have such groups positioned meta,ortho, para, or combinations thereof, relative to the position at whichthe R^(a) group is attached. In yet additional embodiments wherein R¹ isa moiety that can be exchanged or modified to control the chemicaland/or electrochemical properties of the compound, each R¹ can beselected from electron-donating groups, such as those described abovefor R^(a); and R¹ also can be selected from electron-withdrawing groups(e.g., CN, halogen, nitro, ester, etc.).

Exemplary compounds meeting Formulas 1-3 are provided below:

In some embodiments, the methods disclosed herein can be used to producenanostructures, such as nanoribbons having a Formulas 6 or 7.

With reference to Formulas 6 and 7, each X independently can be selectedfrom hydrogen or a terminal functional group and m can range from 1 to1,000 or higher. Each or R¹, R^(a), and n can be as recited above. Insome embodiments, each R¹ independently can be selected from hydrogen,aliphatic, aryl, heteroaliphatic, or heteroaryl; each R^(a)independently can be selected from aryl; aryl substituted with one ormore functional groups selected from aliphatic, alkoxy, amide, amine,thioether, haloalkyl, nitro, halo, silyl, cycloaliphatic, aryl, and thelike; or an electron-donating group; and each n independently can be 1,2, or 3. Suitable terminal functional groups can be selected fromfunctional groups, such as —SO₃CH₃, —SO₃CF₃, halogen, or the like. Insome embodiments, where R^(a) is aryl substituted with one or morefunctional groups, the one or more functional groups can be positionedmeta, ortho, para, or combinations thereof, relative to the position atwhich the R^(a) group is attached. In some embodiments, m can range from2 to 500 or higher, or from 3 to 100 or higher, or from 4 to 50 orhigher. In exemplary embodiments, m ranges from 10 to 80. Exemplarycompounds satisfying Formulas 6 and 7 are illustrated below.

IV. Methods of Making Compounds

Disclosed herein are methods of making pyrene compounds,peropyrene-based compounds, and polymeric compounds satisfying theformulas described above.

Methods of making pyrene compounds are described below in Scheme 1. Withreference to Scheme 1, 2,6-bis[(4-“R”-phenyl)ethynyl]biphenyl 104 wasprepared and then subjected to cyclization conditions using a variety ofBrønsted acids for the purpose of invoking a double cyclizationreaction, presumably via monocyclized intermediate 106, to produce4,10-diarylpyrene derivatives 108.

Results from embodiments using trifluoroacetic acid and differentsolvent systems and conditions are provided by Table 1. In someembodiments, it was determined that after treating 104 with 10equivalents methanesulfonic acid or p-toluenesulfonic acid for 1 day inanhydrous CH₂Cl₂ at room temperature, 108 could be obtained in highyield, such as 60% or 73% yield, separately (see, for example, entries 4and 5 in Table 1). All the results indicated that the strength of theacid had a direct effect on the yield of pyrene. Triflic acid resultedin the rapid (within 5 minutes) formation of pyrene 108 at −40° C. withno detection of mono-cyclized 106 in the crude product, and 108 wasobtained in nearly quantitative yield (Entry 6, Table 1). Without beinglimited to a particular theory of operation, it is currently believedthat the efficiency and yield of the reaction significantly improvedwith increasing acidity of Brønsted acid.

TABLE 1 Brønsted acid screening for the cyclization of 104 Entry AcidSolvent T (° C.) 108^(a) (%) 1 TFA DCM 25  0 2 TFA DCM 50  25b 3 TFA DCE85  52b 4 methane-sulfonic acid DCM 25 60 5 p-toluene-sulfonic acid DCM25 73 6 triflic acid DCM −40 99 ^(a)Isolated yield; ^(b)Yield wasdetermined by crude ¹H NMR.

In some embodiments, additional pyrene and pero-pyrene based compoundsare made using methods described below. As illustrated in Scheme 2, astarting diyne compound 206 can be made using the method stepsillustrated below. In some embodiments, starting material 200 ishalogenated to provide halogenated compound 202. Reaction of halogenatedcompound 202 with suitable reagents to effect an aromatic substitutionreaction (e.g., reagents suitable for a radical-based aromaticsubstitution reaction) can provide compound 204, which can then becross-coupled with two alkyne moieties to provide diyne 206.

With reference to Scheme 2, R¹ can be as recited herein; R² can be anamine (e.g., NH₂); each of X and Y independently can be selected from ahalogen, such as I, Br, F, and Cl; and each R group independently can beas recited herein. In exemplary embodiments, R¹ is hydrogen or alkyl, R²is NH₂, X is I, and Y is Br. An exemplary embodiment of theabove-described method is provided below in Scheme 3.

The synthesis illustrated in Scheme 3 started with iodination of4-tert-butylaniline 300 to give 4-tert-butyl-2,6-diiodoaniline 302followed by Sandmeyer reaction to give compound 304. Compound 304 wasthen subjected to a double cross-coupling reaction with an electron-richalkyne to provide the 1-bromo-2,6-dialkynyl compound (306).

In some embodiments, diyne 206 can be converted to a suitable polymerprecursor using a boronic acid-based coupling method as illustrated inScheme 4. In some embodiments, the boronic acid-based coupling comprisesexposing diyne 206 to a boronic pinacol ester, such as compound 402(where R⁵ is B[—OC(R⁶)₂C(R⁶)₂O—], wherein each R⁶ independently isselected from hydrogen, aliphatic, or aryl) to produce polymer precursor406. In some embodiments, a halogen-metal exchange reaction using ametal-containing compound followed by boronic acid or boronic esterformation can be used to produce compound 400, which can then undergo apalladium-based reaction to provide 2,6-dialkynylbiphenyl derivative 406using bromo compound 404. In yet other embodiments, the2,6-dialkynylbiphenyl derivative 406 can be prepared directly bycoupling diyne 206 with boronic pinacol ester 402. Diyne 406 can then becyclized using an acid to form a pyrene product 412. Exemplary acidsinclude, but are not limited to, HCO₂CF₃, HOSO₂CH₃, HOSO₂CF₃, and thelike. In some embodiments, incomplete cyclization can provide compound408, but this product can be avoided by allowing the reaction mixture towarm to room temperature from a lower temperature (e.g., 0° C. orlower).

With reference to Scheme 4, each of R¹, Y, and Ar are as described abovefor Scheme 2; R⁴ is a boronic acid; and R⁵ is a boronic ester. In someembodiments, R⁴ is B(OH)₂. In some embodiments, R⁵ isB[—OC(R⁶)₂C(R⁶)₂O—], wherein each R⁶ independently is selected fromhydrogen, aliphatic, or aryl. In exemplary embodiments, R⁵ isB[—OC(CH₃)₂C(CH₃)₂O—]. In some embodiments, boronic ester or boronicacid formation can include exposing compound 206 to a metal-containingcompound (e.g., n-BuLi, s-BuLi, t-BuLi, and the like) in solvent tofacilitate halogen-metal exchange, followed by coupling of a boronicacid or a boronic ester (e.g., a boronic ester having a formuladescribed above). In exemplary embodiments, a boronic ester, such as apinacol boronic ester, is used. Cross-coupling reactions, such as thoseillustrated in Scheme 4, can comprise using a palladium-based reagent tofacilitate coupling of a boronic ester compound or a boronic acidcompound (e.g., compound 402) with compound 206. In yet some otherembodiments, cross-coupling can comprise using a palladium-based reagentto facilitate coupling of compound 400 with a halogenated couplingpartner, such as compound 404. Suitable palladium-based reagentsinclude, but are not limited to, Pd(PPh₃)₄, Pd(OAc)₂, PdCl₂, Buchwaldpalladium reagents (e.g., XPhos Pd, SPhos Pd, RuPhos Pd, CPhos Pd, andthe like), or Hartwig palladium reagents (e.g.,Bis(tris(2-tolyl)phosphine)palladium Pd[(o-tol)₃P]₂, QPhos Pd, and thelike). Exemplary embodiments of the methods illustrated in Scheme 4 areillustrated in Scheme 5.

In the exemplary embodiments illustrated in Scheme 5, Suzukicross-coupling conditions were used. In some embodiments, cross-couplingreaction between 306a and 4-tert-butylphenylboronic acid pinacol ester502 resulted in trace formation of desired 2,6-diynylbiphenyl product506. In some embodiments, different coupling partners were evaluated byconverted compound 306a into boronic acid pinacol ester 500, which wassuccessful in cross-coupling with 4-tert-butylbromobenzene 504 toprovide the 2,6-diynylbiphenyl 506 in moderate yield. The synthesis ofsubstrate 506 allows determination of whether double cyclization wasfeasible and also to determine the regioselectivity of cyclization. Insome embodiments, double cyclization of compound 506 involved using acatalytic amount of methanesulfonic acid at 0° C. The monocyclizedphenanthrene product 508 can be formed, but in some embodiments can be aslow conversion. Increasing the amount of acid can improve the reactionspeed significantly. The reaction can be completed within 10 minuteswhen using 2 to 3 equivalents of acid, which resulted in the exclusiveformation of the monocyclized phenanthrene product 508 in nearquantitative yield with no detection of the 5-membered productregioisomeric product 510. Warming the reaction to the room temperaturedid result in double cyclization to provide a pyrene product 512.5-membered ring products 510 and 514 were not detected in mostembodiments, but can potentially be isolated. In some embodiments, thecoupling partners can be adjusted by converting compound 306a into aboronic acid pinacol ester using 502, which was successful in crosscoupling with 1,4-diiodobenzene to provide the2′,2″,6′,6″-tetraynylterphenyl derivative 506 in moderate yield.

In yet additional embodiments, peropyrene-based compounds can be formedusing methods illustrated in Scheme 6. As with Schemes 4 and 5, ahalogen-metal exchange reaction and a boronic ester (or boronic acid)coupling reaction sequence can be used to make compound 602. Compound400 can be cross-coupled with a di-halogenated aryl compound, such ascompound 600 illustrated in Scheme 6. This cross-coupling providesterphenyl derivative 602. Treatment of terphenyl derivative 602 with anacid at a first temperature provides intermediate 604. Treatment ofintermediate 604 with another acid at a second temperature provides thefully cyclized peropyrene compound 606. In some embodiments, the use ofa subsequent acid-catalyzed reaction is used to convert intermediate 604to the desired peropyrene product.

Exemplary embodiments of the methods illustrated in Scheme 6 areillustrated below in Scheme 7. In some embodiments, bis-cyclizedintermediate 704b was obtained in 97% yield while TFA was added at roomtemperature, which was proved by NMR and X-ray crystal analysis. Afterscreening various other Brønsted acids, it was determined that thetetra-cyclized product 706b (and other compounds like 706a, 706c, and706d) could be formed cleanly and rapidly without any acidolysiscompounds while using 2 equivalent of triflic acid (TfOH) at −40° C. Insome embodiments, the bis-cyclization/tetra-cyclization sequence can becarried out as a “one-pot” process. In some embodiments, the one potprocess can result in isolating 706a and 706c in 38% and 45% yield from2′,2″,6′,6″-tetraynylterphenyl derivatives 702a and 702c, respectively(Scheme 7).

In some embodiments, the progress of the reactions described in Schemes6 and 7 above can be observed using thin layer chromatography. Theintermediates obtained from such reactions can be characterized usingvarious techniques, which are disclosed herein. Such intermediates areillustrated in Scheme 8. Some intermediates illustrated below can beavoided using the methods disclosed herein thereby illustrating thereaction product control that is provided by the disclosed methods andestablishing the feasibility of their use on commercial scale.

The bis-cyclized intermediates produced using the methods describedabove can be further converted to peropyrene products usingacid-catalyzed cyclization reactions. In some embodiments, an acid, suchas CF₃SO₃H, or any Brønsted acid having a pKa substantially similar toCF₃SO₃H, such as triflimidic acid (HNTf₂), methane sulfonic acid,benzene sulfonic acid, p-toluene sulfonic acid, and the like, can beused to cyclize bis-cyclized intermediates to peropyrene-basedcompounds. In some embodiments, low temperatures (e.g., below ambienttemperatures, such as from above −100° C. to below 25° C., or above −50°C. to below 10° C., or −40° C. to below 0° C.) can be used during theacid-catalyzed conversion of bis-cyclized intermediate toperopyrene-based compounds.

In particular disclosed embodiments, the course of the reactionillustrated in Scheme 8 can be observed clearly by thin layerchromatography and the intermediates characterized by various techniquesdiscussed herein. Scheme 8 illustrates various possible intermediates.The speed of the first two cyclizations between rings A and B andbetween B and C can be attributed to the flexibility of the substrateand free-rotation of the terphenyl benzene rings, which would allow forgood orbital overlap of the newly forming carbon-carbon bond on rings Dand E. Once ring D is formed to produce a planarized phenanthryl moiety,the second alkyne cyclization between rings A and B is rendered moredifficult due to poor orbital overlap (Scheme 8). With free-rotationstill possible between rings B and C, the second cyclization also can berapid to produce ring E giving intermediate 704. The formation ofintermediate 712 was not observed. Intermediate 704 can be isolated andX-ray crystallographic analysis can be used to confirm its structure.Compound 704 is axially chiral. From the structure of 704, there may bea preference for the third and fourth cyclizations to generate rings Fand G to occur from the opposite direction to produce the axially chiralenantiomers 706 as opposed to the meso compound 718. Compound 716 canundergo a fourth cyclization to give the tetra-cyclized product 706rapidly. Additional exemplary methods of making the compounds disclosedherein are provided by Schemes 9-14.

Using the methods described in Schemes 13 and 14, aromatic ring systemscan be extended from the non-K-region without changing the width of thefused aromatic backbones, a feature that has not been accomplished byconventional methods. With reference to Scheme 14, a bis-cyclizationreaction of compound 1402 can be performed to make peropyrene-basedcompound 1406. As shown in Scheme 14, compound 1402 was isolated in 76%yield by Suzuki coupling reaction of 2,6-dialkynebenzene pinacolboronate 1400 with 2-bromopyrene 1300a. Compound 1402 provided the monobenzannulated product 1404 almost quantitatively in the presence ofexcess trifluoroacetic acid (TFA) at room temperature. As determinedfrom the ¹H NMR of compound 1404, the proton in the cove positionprovides a sharp singlet signal around 11.12 ppm (H₁, Scheme 14).Without being limited to a particular theory, it is currently believedthat this extreme deshielding is attributed to the planarizedphenanthryl geometry formed in compound 1404 after the first cyclizationplacing H₁ in the deshielding zone of the remaining alkyne. In someembodiments, compound 1406 was not observed in the presence of TFA atroom temperature, even after long reaction times. No change in thereaction was observed after adding triflic acid (TfOH) (1 equiv.) to thesolution at −78° C.; however, upon warming the reaction to −40° C., thesecond alkyne cyclization completed instantly, resulting in peropyrene1406.

In particular disclosed embodiments, the peropyrene-based productsdisclosed herein can be made enantioselectively. As indicated herein,the formation of the bis-cyclized intermediates disclosed herein israpid and these intermediates also are axially chiral. Therefore, theinventors of the present disclosure have discovered that it is possibleto invoke a double cyclization to produce chiral peropyrene-basedcompounds using a mild, chiral Brønsted acid.

In additional embodiments, the methods described above in Schemes 1-8can be used and/or modified to make long, polymericperopyrene-containing products, such as nanostructures (e.g., graphenenanostructures or graphene-like nanostructures). In some embodiments,alternative methods to those described in Scheme 2 can be used to obtaincompound 206. For example, starting material 1500 can be converted totriazene compound 1502, followed by selective double palladium-basedcross-coupling to afford dialkynyltriazene 1504. Conversion of thedialkynyltriazene 1504 to intermediate 206 was achieved by treatingdialkynyltriazene 1504 with an alkyl halide. Halogenated intermediate206 was treated with BuLi to effect a lithium-halogen exchange andtrimethoxyborane was added and worked up under acidic conditions toprovide boronic acid 1506 in good yield. Conversion of boronic acid 1506to the pinacol ester 1508 can be conducted using a suitable diolcompound.

With respect to Scheme 15, each of R¹, R², X, Y, and R^(a) can be asrecited herein. In some embodiments, R¹ can be a halogen selected fromBr, I, F, or Cl, or OTf. In some embodiments, each R³ independently canbe selected from hydrogen, aliphatic or aryl; R⁴ is a boronic acid; andR⁵ is a boronic ester. In some embodiments, R¹ is Br. In someembodiments, R³ is selected from alkyl, alkenyl, alkynyl, or aryl. Insome embodiments, R⁴ is B(OH)₂. In some embodiments, R⁵ isB[—OC(R⁶)₂C(R⁶)₂O—], wherein each R⁶ independently is selected fromhydrogen, aliphatic, or aryl. In exemplary embodiments, R³ can beselected from methyl, ethyl, propyl, butyl, pentyl, or the like. Inexemplary embodiments, R⁵ is B[—OC(CH₃)₂C(CH₃)₂O—]. An exemplaryembodiment of the method illustrated in Scheme 15 is provided below inScheme 16.

With respect to the embodiment illustrated in Scheme 16, the synthesisof compound 1610 started with the conversion of aniline 1600 to triazenecompound 1602 followed by selective double Sonogashira cross-coupling toafford dialkynyltriazene 1604. Conversion of dialkynyltriazene 1604 tobromoiododialkynylbenzene 1606 was achieved by treatingdialkynyltriazene 1604 with methyl iodide. Bromoiododialkynylbenzene1606 was treated with BuLi to effect a lithium-halogen exchange andtrimethoxyborane was added and worked up under acidic conditions toprovide boronic acid 1608 in good yield. Conversion of boronic acid 1608to boronic ester 1610 was done in excellent yield.

The pinacol boronic ester (or boronic acid) intermediates disclosedabove in Schemes and 16 can be polymerized to provide intermediatepolymeric products that can then be converted to nanostructuredcompounds as illustrated in Schemes 17A and 17B below. For example, asillustrated in Schemes 17A and 17B, intermediate 400 can be converted topolymer intermediate 1700 using a palladium coupling reaction. Gelpermeation chromatography can be used to analyze polymer 1700, todetermine the polydispersity index (PDI). Upon exposure of polymerintermediate 1700 to an acid, nanostructured compound 1702 can beobtained. An exemplary method is illustrated in FIG. 17B.

Exemplary embodiments of the methods illustrated in Schemes 17A and 17Bare illustrated below in Schemes 18A and 18B. As illustrated in Schemes18A and 18B, pinacol boronic ester 700 is subjected it to Suzukipolymerization conditions to provide alkynyl-substitutedpoly(p-phenylene) polymer 1800 (where Ar is phenyl). Gel permeationchromatography was used to analyze polymer 1800, to determine thepolydispersity index, with some embodiments having a PDI of 1.87 (intoluene) and 1.39 (in THF). The cyclization of the alkynes wassuccessful using trifluoroacetic and triflic acid to provide polymer1802 (where Ar is phenyl). The conversion of polymer 1800 to polymer1802 was confirmed by ¹H and ¹³C NMR, IR, and Raman spectroscopicanalysis. An additional embodiment is shown in Scheme 18B, whereindifferent terminating groups are used to terminate the polymer.

In some embodiments, the choice of reaction solvent (e.g., toluene vsTHF) can influence the difference on the molecular weights obtainedafter polymerization. In some embodiments, a polar solvent, such as THFcan be used to achieve where higher molecular weights are achieved usingTHF (see Table 2 below). In some embodiments, complete benzannulationwas observed after 24 hours using excess TFA at room temperature.Without being limited to a particular theory of operation, it iscurrently believed that this higher reactivity is due to the increasedflexibility of the polymer and partially cyclized intermediates. In aflexible system, such as the partially cyclized intermediates from 1800and even 1802 itself, the ability to “twist” allows for better orbitaloverlap, making benzannulation more facile (FIG. 47). Althoughsignificant cyclization of 1800 was observed according to the ¹H NMR,complete cyclization can be achieved, in some embodiments, by coolingthe reaction mixture to −40° C. and adding a few drops (e.g., 1 to 10drops) of triflic acid. The average length of the 1800 is estimated tobe about 6 nm (toluene) and 20 nm (THF) based on the M_(w) of the 1800isolated. There was no change in the molecular weight distribution ofthe 1802, which indicates that no intermolecular reactions occurredduring the benzannulation reaction.

TABLE 2 Entry Solvent T(h) M_(w) (kgmol⁻¹) M_(n)(kgmol⁻¹) PDI 1Toluene/H₂O 84 6.6 4.6 1.6 2 — — 6.4 4.7 1.4 3 THF/H₂O 48 21.1 10.8 2.04 — — 22.5 11.6 1.9 5 THF/H₂O 132  41.9 28.9 1.5 6 — — 38.2 24.6 1.6With reference to Table 2, M_(w) and M_(n) were determined by SECanalyses of polymer precursor compounds like compound 1800 as obtainedafter the polymerization (eluent: THF). M_(w) and M_(n) are resultsbased on PS standard calibration, respectively. PDI values werecalculated by M_(w)/M_(n). Entry 2 represents results obtained fromanalyzing the polymer promoted by TFA using the polymer from entry 1 asa precursor. Entry 4 is the polymer promoted by MSA using the entry 3polymer as a precursor. Entry 5 is the polymer promoted by TFA-TfOHusing the entry 4 polymer as a precursor.

In some embodiments, gel permeation chromatography (GPC) analysis ofcompound 1800 with a polystyrene (PS) standard indicated anumber-average molecular weight of M_(n)=4.36 kg mol⁻¹ (toluene) and11.2 kg mol⁻¹ (THF) and a weight average molecular weight M_(n)=6.1 kgmol⁻¹ (toluene) and 20.8 kg mol⁻¹ (THF), with a polydispersity index(PDI) of 1.87 (toluene) and 1.39 (THF).

In some embodiments, the conversion of 1800 to polymer 1802 wasconfirmed by ¹H and ¹³C NMR spectroscopic analysis (e.g., FIGS. 35 and36). The disappearance of the peak at 8.32 ppm in the ¹H NMR for polymer1800 (attributed to Hx, see FIG. 35) and the alkyne signals (88.1 and94.1 ppm, see FIG. 36) in the ¹³C NMR. In some embodiments, thedisappearance of the alkyne signal in the IR spectra of polymer 1800 andGNR 1802 and integration can be interpreted as corroborating thatcyclization has occurred, with some embodiment confirming greater than95% cyclization had occurred (e.g., see FIGS. 37 and 38).

In some embodiments, the Raman spectrum of nanostructured compound 1802exhibits the signature features that would be expected for a graphenenanoribbon, such as a D-band (at 1300-1500 cm⁻¹), a G-band (at 1500-1600cm⁻¹), a 2D-band (at 2600-2800 cm⁻¹) and a D+G-band (at 2900-3000 cm⁻¹).In a representative embodiment, the Raman spectrum of 1802 contains thesignature features for GNRs (11, 14, 26), which showed the typicalD-band (1345 cm⁻¹) and G-band (at 1595 cm⁻¹) (FIGS. 26 and 27).Well-resolved double resonant signals were also observed at 2690, 2940,and 3190 cm 1, which can be assigned to 2D, D+G, and 2G bands,respectively. Furthermore, there is a distinct peak ˜235 cm⁻¹ that canbe attributed to the radial breathing-like mode (RBLM) indicating highuniformity of the width of polymer 1802.

In yet additional embodiments, MALDI-TOF mass spectrometry can be usedto confirm that some embodiments of the polymeric structures take on ananoribbon structure, as isotopic patterns corresponding to predicteddistributions can be observed. In yet additional embodiments, thestructure of polymer 1802 can also characterized by UV-vis spectroscopicanalysis. For example, in some embodiments, the UV-vis spectrum of 1800in CH₂Cl₂ solution exhibited a relatively high energy and sharpabsorbance (λ_(max)=309 nm). After benzannulation, it was observed that1802 absorbs from the UV region beyond the visible region and into thenear IR (FIG. 28). There is a low-energy broad absorption with aλ_(max)˜700 nm (1.77 eV) and trails off to and absorption edge ˜1200cm⁻¹ (1.03 eV).

In yet additional embodiments, transmission electron microscopy (TEM)can be conducted on the compound disclosed herein (such as illustratedby FIGS. 39A-39G). In some embodiments, a polymer sample is deposited onlacey carbon grids. At low magnification, the polymeric compounds can bein the form of a large thin film that likely arise from polymeragglomeration during solvent evaporation (See FIG. 39F for an example).In some representative embodiments, the HRTEM images showed areas withmultiple layers of the polymeric compounds (FIGS. 39B, 39C, 39E, and39G). The area with curving layers indicated that the polymericcompounds are flexible (FIG. 39B). In exemplary embodiments, monolayerfilms formed by 1802 were detected, which clearly showed a polymerhaving a single strip (or ribbon) of 1802 (FIGS. 39E and 39G). The widthof 1802 is about 0.5 nm and is in agreement with the theoretical value.The distance between two ribbons of 1802 is narrower (ca. 0.2 nm) thanthe width of 1802 when the side-chains are included, indicating thatthere can be partial stacking of the nanostructures. The bundle ofpolymeric compounds shown in FIG. 39G range from about 8-25 nm, which isconsistent with the calculated result from GPC. The selected areaelectron diffraction (SAED) pattern obtained from polymer 1802demonstrated crystallinity of the sample and revealed hexagonal patternstypical of graphene (FIG. 39D).

In yet additional embodiments, scanning tunneling microscopy (STM)images of polymeric compounds disclosed herein at the solid-liquidinterface of highly oriented pyrolytic graphite(HOPG)/1,2,4-trichlorobenzene (TCB) can be obtained. After deposition ofnanostructures (e.g., 1802) from a TCB dispersion on the HOPG substrate,the nanostructures showed side by side aggregation, also seen by TEM(FIGS. 40, 39E and 39G). The nanostructures also showed extension alongone-dimensional direction, which were observed to be over 100 nm inlength (FIG. 40). The length (7 20 nm, FIG. 40) of the ribbons is inagreement with the results from the GPC and TEM characterizationmethods. The pattern seen in the STM images showed regions ofalternating height, implying that the aryl substituents on the ribbonare alternating up and down, which may be explained by two kinds ofintramolecular H . . . H repulsion: one from the two phenyl groups offthe backbone, and one from the phenyl group and the bay region hydrogen,which result in a significant tilt of the latter with respect to thesurface (e.g., FIG. 40). Semi empirical methods (PM3) were used for ashort model of 1802 to better understand this alternating pattern. Theresult supports that the aryl groups are alternating up and down (e.g.,FIG. 40). The observed periodicity (˜1.16 nm) of the aryl substituentscorresponded closely to the longitudinal length of one repeating unit(˜0.9 nm), and the width (˜1 nm, including two phenyls off the backbone,FIG. 40) of nanostructures of 1802 was also close to the calculatedvalue (ca. 1.1 nm).

IV. Examples

General Experimental Section—

Chemicals and solvents were purchased from Oakwood Products Inc., andSigma-Aldrich and used directly without further purification unlessotherwise stated. Anhydrous tetrahydrofuran (THF) and dichloroethane(DCM) was obtained by passing the solvent (HPLC grade) through anactivated alumina column on a JC Meyer solvent drying system. Allreactions dealing with air- or moisture-sensitive compounds were carriedout in a dry reaction vessel under nitrogen.

¹H and ¹³C NMR spectra were recorded on Varian 400 MHz or Varian 500 MHzNMR Systems Spectrometers. Spectra were recorded in deuteratedchloroform (CDCl₃). Tetramethylsilane (TMS, set to 0 ppm) was used as aninternal standard for chemical shifts. Solvent peaks (7.26 ppm for ¹Hand 77.16 ppm for ¹³C, respectively) as reference. Chemical shifts arereported in part per million (ppm) from low to high frequency andreferenced to the residual solvent resonance. Coupling constants (J) arereported in Hz. The multiplicity of 1H signals are indicated as:s=singlet, d=doublet, t=triplet, dd=double doublet, m=multiplet,br=broad.

Mass spectra were recorded using an Agilent 6230 TOF MS. The instrumentwas operated with an atmospheric pressure photoionization (APPI) sourceon a time of flight (TOF) instrument in the positive mode. Toluene wasadded to samples to promote ionization.

UV-visible and fluorescence spectra were acquired at ambienttemperature; λ in nm (ε in L·mol⁻¹·cm⁻¹).

High resolution ESI mass spectrometry was recorded using an Agilent 6230TOF MS. TFA was added to samples to promote ionization.

Solution UV-vis absorption spectra were recorded at room temperature ona Perkin-Elmer Lambda 900 spectrophotometer.

With reference to Scheme 8, various techniques can be used to determinethe products and intermediates involved in making the peropyrenecompounds disclosed herein. In some embodiments, ¹H NMR, UV-vis andfluorescence spectra showed big difference. From the ¹H NMR spectracomparison, it was determined that planarized picene moiety was formedin the bis-cyclized product, due to the deshielding effect of thealkyne, the signals for the proton in the cove position exhibitedsubstantial downfield-shift to 10.39 ppm (12b, FIG. 48A). Besides, abroad peak appeared in the aromatic region should be attributed to thetwo phenyl rings on the picene moiety. This is because the Ar groups aretoo close to each other which limit their free rotation. The broad peakshowed no correlation with the other two phenyl groups connection on thealkynes in the ROESY and NOESY spectra, which also confirmed that nointermediate 712 or 714 formed (FIGS. 2 and 3, respectively). Thedeshielding effect of the alkyne got stronger while the whole systembecame more planarized in the tri-cyclized product, which leaded moredownfield-shift of the signal for the proton in the cove position to10.71 ppm (12c, FIG. 48A). The ¹H NMR of methoxyl groups exhibited muchmore directly, which showed one singlet in compounds 702a-d and 704a-dbecause they were center symmetrical, while showed two singlets inaxisymmetric compound 702a-d and four different singlets in unsymmetriccompound 708a-d (FIG. 48B).

As the cyclization reaction gradually completed, the whole compoundskeleton became more and more conjugated, which was clearly reflected byUV-vis absorption and fluorescence emission spectrum (FIGS. 4 and 5).Additional images of representative compounds, including absorption andfluorescence spectra are provided by FIGS. 8 and 9. From the UV-visabsorption spectra, the maximum absorption peaks were observed as movingto the longer wavelengths with the cyclization completion (293, 345, 510nm). The maximum emission peaks moved to the longer wavelengths too(389, 432, 530 nm).

Synthesis and Characterization Synthesis of Pyrene Compounds

Compound R Acid Amount Temp Time 4:5 Yield 108a 4-OMe—C₆H₄ TFA ExcessReflux 2 Days 4:5 <50%  4-OMe—C₆H₄ CF₃SO₃H Excess 0° C. 5 min 0:1 <50% 4-OMe—C₆H₄ CF₃SO₃H 10 mol % RT 1 Hour 1:0 70% 4-OMe—C₆H₄ (CF₃SO₂)₂NH 10mol % RT 30 min 0:1 48% 108b 4-O-ethylhexyl-C₆H₄ CF₃SO₃H 10 mol % RT 24hours 0:1 80% 4-O-ethylhexyl-C₆H₄ CF₃SO₃H 10 mol % RT 3 hours 0:1 82%4-O-ethylhexyl-C₆H₄ (CF₃SO₂)₂NH 10 mol % RT 24 hours 0:1 54%4-O-ethylhexyl-C₆H₄ (CF₃SO₂)₂NH 10 mol % RT 3 hours 0:1 63% 108c4-N(CH₃)₂C₆H₄ 108d C₆H₅ (CF₃SO₂)₂NH 10 mol % Reflux 16 hours 1:0 25%C₆H₅ CF₃SO₃H 10 mol % RT 108e 4-BrC₆H₄ (CF₃SO₂)₂NH 10 mol % 60° C. 1Hour 1:0 108f 4-NO₂C₆H₄ CF₃SO₃H Excess 60° C. 24 hours 0:0  0% 108g4-CF₃C₆H₄ CH₃SO₃H Excess RT 30 min 0:0  0% 4-CF₃C₆H₄ (CF₃SO₂)₂NH 10 mol% 60° C. 18 hours 0:0 Decomposed 4-CF₃C₆H₄ CF₃SO₃H Excess RT 1 hour 0:0Decomposed  8 TMS (CF₃SO₂)₂NH 10 mol % RT 5 min — H Pdt  9 H (CF₃SO₂)₂NH10 mol % RT 24 hours — Addition Pdt  10 C₆H₁₃

Compound 104a: To a solution of 100 bis triflate (1.0 g, 2.22 mmol) inanhydrous DMF (75 mL) was added 102a (0.681 g, 5.15 mmol),Bis(triphenylphosphine)palladium II dichloride (0.324 g, 0.462 mmol),Tetraethylammonium iodide (1.15 g, 4.47 mmol), triethylamine (4.02 mL,54.7 mmol), and copper (I) iodide (0.180 g, 0.945 mmol) in that order.The flask was heated to 85° C. and stirred until it was confirmedcomplete by TLC; ca. 18 hours. The reaction was quenched with saturatedaqueous ammonium chloride at room temperature, taken up in 100 mLdiethyl ether, and the layers separated. The organic phase was washedwith saturated aqueous ammonium chloride (3×50 mL), brine (3×50 mL),dried over MgSO₄, and the mixture filtered. The solvent was removed invacuo and the crude product purified by column chromatography (silicagel, 1:1 CH₂Cl₂/benzene) to yield 104a (446 mg, 48%) as an whitecrystalline solid: ¹H NMR (400 MHz, CDCl₃): δ 7.55-7.51 (m, 2H), 7.46(d, 2H), 7.41-7.30 (m, 3H), 7.18 (t, 1H), 7.07-7.02 (m, 4H), 6.69-6.65(m, 4H), 3.65 (s, 6H); ¹³C NMR (500 MHz, CDCl₃): δ 143.1, 139.6, 139.1,136.6, 130.6, 129.6, 127.9, 127.7, 127.0, 112.6, 0.2.

Compound 104b: To a solution of 100 (0.539 g, 2.67 mmol) in THF (50 mL)was added 102b (1.79 g, 5.63 mmol), Bis(triphenylphosphine)palladium IIdichloride (0.096 g, 0.137 mmol), triethylamine (1.86 mL, 13.3 mmol),and copper (I) iodide (0.105 g, 0.551 mmol) in that order. The flask wasleft at room temperature and stirred until it was confirmed complete byTLC; ca. 18 hours. The reaction was quenched with saturated aqueousammonium chloride at room temperature, taken up in 100 mL diethyl ether,and the layers separated. The organic phase was washed with saturatedaqueous ammonium chloride (3×50 mL), brine (3×50 mL), dried over MgSO₄,and the mixture filtered. The solvent was removed in vacuo and the crudeproduct purified by column chromatography (silica gel, 1:5CH₂Cl₂/Hexane) to yield 104b (552 mg, 34%) as yellow oil. ¹H NMR (500MHz, CDCl₃): δ 7.64-7.60 (m, 2H), 7.56 (d, 2H), 7.51-7.40 (m, 3H), 7.29(t, 1H), 7.15-7.10 (m, 4H), 6.81-6.76 (m, 4H), 3.85-3.78 (m, 4H),1.76-1.67 (m, 2H), 1.55-1.25 (m, 18H), 0.96-0.87 (m, 13H); ¹³C NMR (500MHz, CDCl₃): δ 159.4, 145.8, 139.3, 132.7, 131.4, 130.4, 127.4, 127.3,127.0, 123.5, 115.0, 114.4, 93.1, 87.6, 70.5, 53.4, 39.3, 30.5, 29.0,23.8, 23.0, 14.1, 11.1.

Compound 104e: To a solution of 100 (0.503 g, 2.49 mmol) in THF (50 mL)was added 102e (1.76 g, 6.22 mmol), Bis(triphenylphosphine)palladium IIdichloride (0.088 g, 0.125 mmol), triethylamine (1.73 mL, 12.4 mmol),and copper (I) iodide (0.101 g, 0.530 mmol) in that order. The flask wasleft at room temperature and stirred until it was confirmed complete byTLC; ca. 18 hours. The reaction was quenched with saturated aqueousammonium chloride at room temperature, taken up in 100 mL diethyl ether,and the layers separated. The organic phase was washed with saturatedaqueous ammonium chloride (3×50 mL), brine (3×50 mL), dried over MgSO₄,and the mixture filtered. The solvent was removed in vacuo and the crudeproduct purified by recrystallization (super saturate in hot toluene;triturate with cold hexane) to yield 104e (292 mg, 23%) as a beigepowder solid. ¹H NMR (500 MHz, CDCl₃): δ 7.62-7.55 (m, 4H), 7.51-7.41(m, 3H), 7.40-7.36 (m, 4H), 7.33 (t, 1H), 7.05-7.01 (m, 4H); ¹³C NMR(500 MHz, CDCl₃): δ 146.5, 138.9, 132.7, 132.2, 131.5, 130.2, 127.7,127.4, 127.2, 123.0, 122.5, 122.0, 92.0, 89.8.

Compound 104f: To a solution of 100 (0.205 g, 1.01 mmol) in THF (50 mL)was added 102f (0.518 g, 2.08 mmol), Bis(triphenylphosphine)palladium IIdichloride (0.040 g, 0.057 mmol), triethylamine (0.690 mL, 4.95 mmol),and copper (I) iodide (0.046 g, 0.242 mmol) in that order. The flask wasleft at room temperature and stirred until it was confirmed complete byTLC; ca. 18 hours. The reaction was quenched with saturated aqueousammonium chloride at room temperature, taken up in 100 mL diethyl ether,and the layers separated. The organic phase was washed with saturatedaqueous ammonium chloride (3×50 mL), brine (3×50 mL), dried over MgSO₄,and the mixture filtered. The solvent was removed in vacuo and the crudeproduct purified by recrystallization (super saturate in hot toluene;triturate with cold hexane) to yield 104f (270 mg, 60%) as an orangepowder solid. ¹H NMR (500 MHz, CDCl₃): δ 8.15-8.10 (m, 4H), 7.69 (d,2H), 7.60-7.56 (m, 2H), 7.55-7.48 (m, 3H), 7.41 (t, 1H) 7.31-7.27 (m,4H); ¹³C NMR (500 MHz, CDCl₃): δ 147.5, 147.0, 138.6, 133.1, 132.0,130.1, 129.8, 128.1, 127.6, 127.5, 123.5, 122.4, 93.6, 91.3.

Compound 104g: To a solution of 100 (0.500 g, 2.47 mmol) in THF (150 mL)was added 102g (0.910 mL, 6.19 mmol), Bis(triphenylphosphine)palladiumII dichloride (0.089 g, 0.127 mmol), triethylamine (1.72 mL, 12.3 mmol),and copper (I) iodide (0.100 g, 0.525 mmol) in that order. The flask wasleft at room temperature and stirred until it was confirmed complete byTLC; ca. 18 hours. The reaction was quenched with saturated aqueousammonium chloride at room temperature, taken up in 100 mL diethyl ether,and the layers separated. The organic phase was washed with saturatedaqueous ammonium chloride (3×50 mL), brine (3×50 mL), dried over MgSO₄,and the mixture filtered. The solvent was removed in vacuo and the crudeproduct purified by column chromatography (silica gel, 1:6CH₂Cl₂/hexane) to yield 104g (480 mg, 40%) as a beige powder solid. ¹HNMR (500 MHz, CDCl₃): δ 7.65 (d, 2H), 7.61-7.57 (m, 2H), 7.54-7.44 (m,7H), 7.37 (t, 1H), 7.29-7.26 (m, 4H); ¹³C NMR (500 MHz, CDCl₃): δ 147.1,138.8, 138.0, 132.6, 131.5, 130.2, 130.0, 129.7, 127.9, 127.5, 127.3,126.8, 125.2, 125.1, 125.0, 122.7, 91.7, 90.9.

Compound 108a: To a flask containing CH₂Cl₂ (10 mL) was added 50 μL of astock solution (1 mL of triflic acid dissolved in 49 mL CH₂Cl₂ in asealed schlenk tube). To a separate flask containing 104a (0.065 g,0.106 mmol) was added CH₂Cl₂ (10 mL). The resultant solution was takenup in a syringe and was slowly added to the first flask, dropwise, over1 hour at room temperature. The flask was left at room temperature andstirred until it was confirmed complete by TLC; ca. 24 hours. Thereaction was quenched with saturated aqueous sodium hydroxide at roomtemperature and the layers separated. The organic phase was washed withsaturated aqueous sodium hydroxide (2×20 mL), H₂O (2×20 mL), dried overMgSO₄, and the mixture filtered. The solvent was removed in vacuo andthe crude product purified by column chromatography (silica gel, 1:5CH₂Cl₂/hexane) to yield 108a (52 mg, 80%) as a yellow oil. ¹H NMR (500MHz, CDCl₃): δ 8.28 (d, 2H), 8.19 (d, 2H), 8.06-8.02 (m, 3H), 7.91 (t,1H), 7.63-7.59 (m, 4H) 7.10-7.15, 4.03-3.96 (m, 4H), 1.84 (sp, 2H),1.67-1.36 (m, 19H), 1.05-0.95 (m, 13H); ¹³C NMR (500 MHz, CDCl₃): δ159.0, 139.4, 133.0, 131.1, 131.0, 130.8, 127.6, 126.3, 125.4, 125.4,124.7, 124.1, 123.6, 114.4, 39.5, 30.6, 29.1, 24.0, 23.1, 14.1, 11.2.

Compound 108b: To a flask containing CH₂Cl₂ (10 mL) was added 50 μL of astock solution (1 mL of triflic acid dissolved in 49 mL CH₂Cl₂ in asealed schlenk tube). To a separate flask containing 104b (0.065 g,0.106 mmol) was added CH₂Cl₂ (10 mL). The resultant solution was takenup in a syringe and was slowly added to the first flask, dropwise, over1 hour at room temperature. The flask was left at room temperature andstirred until it was confirmed complete by TLC; ca. 24 hours. Thereaction was quenched with saturated aqueous sodium hydroxide at roomtemperature and the layers separated. The organic phase was washed withsaturated aqueous sodium hydroxide (2×20 mL), H₂O (2×20 mL), dried overMgSO₄, and the mixture filtered. The solvent was removed in vacuo andthe crude product purified by column chromatography (silica gel, 1:5CH₂Cl₂/hexane) to yield 108b (52 mg, 80%) as a yellow oil. ¹H NMR (500MHz, CDCl₃): δ 8.28 (d, 2H), 8.19 (d, 2H), 8.06-8.02 (m, 3H), 7.91 (t,1H), 7.63-7.59 (m, 4H) 7.10-7.15, 4.03-3.96 (m, 4H), 1.84 (sp, 2H),1.67-1.36 (m, 19H), 1.05-0.95 (m, 13H); ¹³C NMR (500 MHz, CDCl₃): δ159.0, 139.4, 133.0, 131.1, 131.0, 130.8, 127.6, 126.3, 125.4, 125.4,124.7, 124.1, 123.6, 114.4, 39.5, 30.6, 29.1, 24.0, 23.1, 14.1, 11.2.

Synthesis of Compound 306:

To the solution of 2-bromo-5-(tert-butyl)-1,3-diiodobenzene 304 (4.65 g,10 mmol, 1.0 equiv.) and the terminal alkyne (2.5 equiv.) in Et₃N (40mL) and THF (80 mL), were added Pd(PPh₃)₂Cl₂ (70 mg, 0.1 mmol) and CuI(38 mg, 0.2 mmol). The resulting mixture was stirred under a N₂atmosphere at room temperature for 14 h. The ammonium salt was thenremoved by filtration. The solvent was removed under reduced pressureand the residue was purified by column chromatography (SiO₂, hexane/DCM)to afford the corresponding product 306.

306a (4.3 g, 91%). ¹H NMR (500 MHz, CDCl₃) δ 7.53 (d, J=8.7 Hz, 2H),7.48 (s, 1H), 6.88 (d, J=8.7 Hz, 2H), 3.98 (t, J=6.5 Hz, 2H), 1.83-1.75(m, 2H), 1.45 (m, 2H), 1.31 (m, 17H), 0.89 (t, J=6.8 Hz, 3H). ¹³C NMR(126 MHz, CDCl₃) δ 159.69, 150.14, 133.35, 133.26, 129.80, 126.16,125.06, 114.87, 114.71, 93.71, 87.53, 68.25, 34.70, 32.05, 31.18, 29.73,29.71, 29.55, 29.48, 29.34, 26.17, 22.84, 14.28. HRMS (ESI, positive)m/z calcd for C₂₈H₂₅BrO₂ [M]⁺ 472.1038, found 472.1043 (see FIGS. 10Aand 10B for NMR spectra).

306b (4.3 g, 86%). ¹H NMR (400 MHz, CDCl₃) δ 7.55 (d, J=8.9 Hz, 4H),7.49 (s, 2H), 6.90 (d, J=8.9 Hz, 4H), 3.84 (s, 6H), 1.33 (s, 9H). ¹³CNMR (126 MHz, CDCl₃) δ 160.09, 150.18, 133.48, 133.39, 133.31, 133.24,129.95, 129.85, 129.75, 126.14, 125.10, 115.18, 114.48, 114.39, 114.20,114.02, 113.91, 113.73, 93.60, 87.62, 55.58, 55.39, 34.71, 31.25, 31.18,31.10. HRMS (ESI, positive) m/z calcd for C₂₈H₂₅BrO₂ [M]⁺ 472.1038,found 472.1043 (see FIGS. 11A and 11B for NMR spectra).

306c (5.76 g, 87%). ¹H NMR (400 MHz, CDCl₃) δ 7.55 (d, J=8.9 Hz, 2H),7.51 (s, 1H), 6.91 (d, J=8.9 Hz, 2H), 3.88 (dd, J=5.8, 0.9 Hz, 2H),1.78-1.71 (m, 1H), 1.54-1.41 (m, 4H), 1.37-1.32 (m, 9H), 0.97-0.90 (m,6H). ¹³C NMR (126 MHz, CDCl₃) δ 159.93, 150.11, 133.30, 129.74, 126.20,125.08, 114.81, 114.73, 93.78, 87.53, 77.41, 77.16, 76.91, 70.71, 39.47,34.67, 31.15, 30.64, 29.22, 23.98, 23.18, 14.23, 11.26. HRMS (ESI,positive) m/z calcd for C₄₂H₅₃BrO₂ [M]⁺ 668.3229, found 668.3219 (seeFIGS. 12A and 12B for NMR spectra).

306d (4.24 g, 69%). R_(f)=0.25 (hexane/DCM 10:1). FTIR (neat) 2953,2940, 2208, 1603, 1562, 1508, 1472, 1936, 1284, 1245, 1172, 1024, 829cm⁻¹. ¹H NMR (400 MHz, cdcl₃) δ 7.53 (d, J=8.7 Hz, 4H), 7.49 (s, 2H),6.89 (d, J=8.8 Hz, 4H), 3.98 (t, J=6.6 Hz, 4H), 1.82-1.76 (m, 4H),1.50-1.33 (m, 21H), 0.92 (t, J=6.9 Hz, 6H). ¹³C NMR (100 MHz, cdcl₃) δ159.70, 150.14, 133.35, 129.79, 126.18, 125.07, 114.89, 114.72, 93.73,87.54, 68.26, 34.70, 31.73, 31.17, 29.31, 25.85, 22.75, 14.19.

Synthesis of Compound 700:

To a solution of aryl bromide 306 (10 mmol, 1.0 equiv.) in THF (50 mL)at −78° C. was added a solution of n-butyllithium in hexanes (5 mL, 2.5M, 1.25 equiv.). After stirring for 1 h at −78° C., isopropoxyboronicacid pinacol ester (2.79 g, 15 mmol, 1.5 equiv.) was added, the reactionremoved from the cooling bath and allowed to warm. Upon reaching roomtemperature the reaction was quenched by the addition of H₂O, and thenextracted with DCM. The extract was washed with water, dried withNa₂SO₄, filtered and concentrated in vacuo. The residue was purified byflash column chromatography (SiO₂, hexane/DCM) to afford thecorresponding product 700.

700a (3.49 g, 67%). ¹H NMR (400 MHz, CDCl₃) δ 7.48 (s, 2H), 7.45 (d,J=8.7 Hz, 4H), 6.85 (d, J=8.7 Hz, 4H), 3.96 (t, J=6.6 Hz, 4H), 1.82-1.75(m, 4H), 1.38-1.25 (m, 49H), 0.89 (t, J=6.6 Hz, 6H). ¹³C NMR (126 MHz,CDCl₃) δ 159.26, 152.27, 133.09, 128.75, 126.87, 115.54, 114.58, 89.98,88.84, 84.26, 77.41, 77.16, 76.91, 68.20, 34.78, 32.05, 31.14, 29.72,29.70, 29.54, 29.47, 29.37, 26.19, 25.15, 22.83, 14.26. HRMS (ESI,positive) m/z calcd for C₃₄H₃₇BO₄Na [M+Na]⁺ 543.2683, found 543.2690(see FIGS. 13A and 13B for NMR spectra).

700b (3.49 g, 59%). ¹H NMR (500 MHz, CDCl₃) δ 7.52 (s, 2H), 7.49 (d,J=7.6 Hz, 4H), 6.88 (d, J=7.6 Hz, 4H), 3.80 (s, 6H), 1.36 (d, J=27.2 Hz,21H). ¹³C NMR (126 MHz, CDCl₃) δ 159.64, 152.29, 133.10, 129.65, 128.77,126.83, 115.79, 114.05, 89.87, 88.91, 84.26, 55.39, 34.77, 31.44, 31.12,25.14. HRMS (ESI, positive) m/z calcd for C₃₄H₃₇BO₄Na [M+Na]⁺ 543.2683,found 543.2690 (see FIGS. 14A and 14B for NMR spectra).

700c (4.23 g, 61%). ¹H NMR (400 MHz, CDCl₃) δ 7.53 (s, 1H), 7.50 (d,J=8.9 Hz, 2H), 6.90 (d, J=8.9 Hz, 2H), 3.87 (d, J=5.9 Hz, 2H), 1.78-1.71(m, 1H), 1.56-1.44 (m, 4H), 1.40 (s, 6H), 1.38-1.31 (m, 9H), 0.97-0.91(m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 159.40, 152.04, 132.91, 128.51,126.88, 115.38, 114.49, 89.98, 88.74, 84.05, 70.48, 39.39, 34.57, 31.62,30.99, 30.55, 29.12, 25.01, 23.89, 23.06, 22.68, 14.10, 11.15. HRMS(ESI, positive) m/z calcd for C₄₈H₆₆BO₄ [M+H]⁺ 717.5054, found 717.5053(see FIGS. 15A and 15B for NMR spectra).

700d (4.19 g, 63%). R_(f)=0.20 (hexane/DCM 4:1). FTIR (neat) 2954, 2931,2869, 2205, 1605, 1587, 1508, 1467, 1331, 1315, 1245, 1133, 854, 829cm⁻¹. ¹H NMR (400 MHz, cdcl₃) δ 7.48 (s, 2H), 7.45 (d, J=8.8 Hz, 4H),6.86 (d, J=8.8 Hz, 4H), 3.97 (t, J=6.6 Hz, 4H), 1.81-1.75 (m, 4H),1.46-1.30 (m, 37H), 0.91 (t, J=6.9 Hz, 6H). ¹³C NMR (100 MHz, cdcl₃) δ159.25, 152.25, 133.08, 128.73, 126.86, 115.52, 114.56, 89.97, 88.83,84.25, 68.18, 34.76, 31.72, 31.13, 29.32, 25.85, 25.14, 22.74, 14.17.

Synthesis of Trimer 702:

1,4-diiodobenzene (0.33 g, 1 mmol, 0.5 equiv.), 2,6-diynylphenyl borate700 (2 mmol, 1.0 equiv.) and Ag₂CO₃ (1.1 g, 4 mmol, 2.0 equiv.) weredissolved in anhydrous THF (60 mL). Pd(PPh₃)₄ (231 mg, 0.2 mmol, 0.1equiv.) was added to the solution before degassing the mixture viabubbling nitrogen for 30 min. The resulting mixture was stirred under aN₂ atmosphere at 80° C. for 24 h. After the reaction was complete, themixture was diluted with DCM, washed with H₂O and dried over Na₂SO₄. Thesolvent was removed under reduced pressure and the residue was purifiedby column chromatography (SiO₂, hexane/DCM) to give the desiredhead-to-head Sandwich-like trimer 702.

702a (0.45 g, 57%). ¹H NMR (500 MHz, CDCl₃) δ 7.76 (s, 4H), 7.70 (s,4H), 7.09 (d, J=8.7 Hz, 8H), 6.56 (d, J=8.8 Hz, 8H), 3.80 (t, J=6.6 Hz,8H), 1.74-1.69 (m, 8H), 1.50-1.31 (m, 74H), 0.94 (t, J=6.9 Hz, 12H). ¹³CNMR (126 MHz, CDCl₃) δ 158.95, 150.05, 143.64, 138.80, 132.92, 129.59,128.53, 123.56, 115.04, 114.30, 93.05, 88.22, 67.94, 34.70, 32.05,31.36, 29.73, 29.71, 29.53, 29.48, 29.28, 26.15, 22.83, 14.26. HRMS(ESI, positive) m/z calcd for C₆₂H₅₄O₄ [M]⁺ 862.4022, found 862.4012(see FIGS. 16A and 16B for NMR spectra).

702b (0.45 g, 65%). ¹H NMR (500 MHz, CDCl₃) δ 7.71 (s, 2H), 7.65 (s,2H), 7.04 (d, J=8.8 Hz, 4H), 6.53 (d, J=8.8 Hz, 4H), 3.64 (s, 6H), 1.45(s, 9H). ¹³C NMR (126 MHz, CDCl₃) δ 159.35, 150.15, 143.68, 138.82,132.95, 129.59, 128.62, 123.50, 115.31, 113.77, 92.90, 88.30, 77.41,77.16, 76.91, 55.24, 34.76, 31.38. HRMS (ESI, positive) m/z calcd forC₆₂H₅₄O₄ [M]⁺ 862.4022, found 862.4012 (see FIGS. 17A and 17B for NMRspectra).

702c (0.76 g, 63%). ¹H NMR (500 MHz, CDCl₃) δ 7.72 (s, 1H), 7.66 (s,1H), 7.05 (d, J=8.8 Hz, 2H), 6.54 (d, J=8.8 Hz, 2H), 3.69-3.64 (m, 2H),1.66-1.61 (m, 1H), 1.46 (s, 5H), 1.43-1.28 (m, 10H), 0.93-0.88 (m, 6H).¹³C NMR (126 MHz, CDCl₃) δ 159.22, 150.07, 143.70, 138.81, 132.92,129.61, 128.51, 123.58, 114.98, 114.36, 93.09, 88.20, 77.41, 77.16,76.91, 70.50, 39.39, 34.75, 31.75, 31.39, 30.63, 29.20, 23.95, 23.19,22.81, 14.22, 11.21. HRMS (ESI, positive) m/z calcd for C₉H₁₁₀O₄ [M]⁺1254.8404, found 1254.8371 (see FIGS. 18A and 18B for NMR spectra).

702d (0.76 g, 66%)¹H NMR (400 MHz, cdcl₃) δ 7.78 (s, 4H), 7.71 (s, 4H),7.10 (d, J=8.7 Hz, 8H), 6.58 (d, J=8.8 Hz, 8H), 3.80 (t, J=6.5 Hz, 8H),1.76-1.68 (m, 8H), 1.51-1.34 (m, 42H), 0.95 (t, J=6.8 Hz, 12H). ¹³C NMR(100 MHz, cdcl₃) δ 157.99, 149.51, 139.93, 136.56, 131.59, 128.12,126.09, 124.10, 122.79, 120.43, 68.34, 35.34, 32.06, 31.86, 29.53,25.95, 22.83, 14.26.

Synthesis of Bis-Cyclization Trimer 704b:

In a flame dried flask under a nitrogen atmosphere, 702b (100 mg, 0.11mmol) was dissolved in anhydrous DCM (50 mL), and cooled to 0° C.Methanesulfonic acid (3 drops) was added by syringe to the solution. Thereaction mixture was stirred for 1 h, and then quenched with saturatedNaHCO₃ aqueous solution (1.0 mL). The mixture was washed with H₂O (2×20mL) and dried over Na₂SO₄. The solvent was then removed under reducedpressure and the residue was purified by column chromatography (SiO₂,hexane/DCM, 80/20, v/v) to give the bis-cyclization trimer 704b (97 mg,97%) as yellow solids. ¹H NMR (500 MHz, CDCl₃) δ 10.40 (s, 1H), 8.07 (d,J=2.2 Hz, 1H), 7.85 (d, J=2.1 Hz, 1H), 7.68-7.64 (m, 2H), 7.39 (s, 1H),6.87-6.83 (m, 2H), 6.43-6.78 (br, 4H), 3.82 (d, J=1.9 Hz, 6H), 1.53 (s,9H). ¹³C NMR (126 MHz, CDCl₃) δ 159.81, 158.39, 148.60, 140.11, 136.33,133.38, 132.95, 132.54, 131.38, 128.64, 128.54, 126.49, 125.30, 123.47,119.40, 116.06, 114.34, 94.39, 91.68, 77.42, 77.16, 76.91, 55.49, 55.38,34.76, 31.73, 31.42, 22.80, 14.27. HRMS (ESI, positive) m/z calcd forC₆₂H₅₄O₄ [M]⁺ 862.4022, found 862.4016 (see FIGS. 20A and 20B for NMRspectra). In some embodiments, the structures of 702b, 704b, and 706bwere optimized by Merck Molecular Force Field 94 (MMFF94) calculations(grey, carbon; white, hydrogen; red, oxygen) as illustrated in FIG. 7.

704a and 704c were also can be prepared following the same procedure.

704a: ¹H NMR (400 MHz, CDCl₃) δ 10.36 (s, 2H), 8.03 (d, J=1.9 Hz, 2H),7.81 (d, J=1.8 Hz, 2H), 7.63 (d, J=8.6 Hz, 4H), 7.36 (s, 2H), 6.83 (d,J=8.7 Hz, 4H), 6.48-6.57 (br, 8H), 4.03-3.87 (m, 8H), 1.81 (d, J=6.0 Hz,8H), 1.55-1.21 (m, 74H), 0.90 (m, 12H). ¹³C NMR (126 MHz, cdcl₃) δ159.29, 157.77, 148.38, 140.06, 136.03, 133.25, 132.79, 132.31, 131.22,128.46, 128.42, 126.33, 125.09, 123.32, 119.30, 115.65, 114.72, 94.35,91.46, 68.15, 68.09, 34.61, 31.93, 31.29, 29.64, 29.61, 29.50, 29.48,29.38, 29.36, 29.29, 26.10, 26.09, 22.71, 14.14. HRMS (ESI, positive)m/z calcd for C₆₂H₅₄O₄ [M]⁺ 862.4022, found 862.4016 (see FIGS. 19A and19B for NMR spectra).

704c: ¹H NMR (500 MHz, cdcl₃) δ 10.39 (s, 2H), 8.08 (d, J=2.1 Hz, 2H),7.87 (d, J=2.1 Hz, 2H), 7.68 (d, J=8.8 Hz, 4H), 7.41 (s, 2H), 6.90 (d,J=8.8 Hz, 4H), 6.25-6.71 (br, 8H), 3.92-3.86 (m, 8H), 1.80 (m, 5H), 1.56(s, 21H), 1.52-1.36 (m, 31H), 1.04-0.96 (m, 24H). ¹³C NMR (126 MHz,cdcl₃) δ 159.71, 158.21, 158.20, 148.52, 140.27, 136.13, 133.39, 132.92,132.39, 131.37, 128.65, 128.60, 126.53, 125.19, 123.51, 119.47, 115.73,114.90, 94.50, 91.58, 77.41, 77.16, 76.91, 70.93, 70.91, 70.79, 70.77,39.56, 39.51, 34.76, 31.50, 31.44, 30.73, 30.67, 30.65, 29.30, 29.26,29.24, 24.05, 24.00, 23.99, 23.28, 23.25, 23.24, 23.22, 14.30, 14.25,11.30, 11.29, 11.27, 11.26. HRMS (ESI, positive) m/z calcd for C₆₂H₅₄O₄[M]⁺ 862.4022, found 862.4016 (see FIGS. 21A and 21B for NMR spectra).

704d (97 mg, 97%)¹H NMR (400 MHz, cdcl₃) δ 10.35 (s, 2H), 8.02 (s, 2H),7.80 (s, 2H), 7.61 (d, J=7.4 Hz, 4H), 7.35 (s, 2H), 6.81 (d, J=8.3 Hz,4H), 6.52 (br, 8H), 3.97-3.86 (m, 8H), 1.83-1.74 (m, 8H), 1.50-1.33 (m,42H), 0.92 (d, J=2.4 Hz, 12H). ¹³C NMR (100 MHz, cdcl₃) δ 159.43,157.90, 148.53, 140.20, 136.15, 133.39, 132.92, 132.45, 131.35, 128.59,128.55, 126.46, 125.22, 123.46, 119.44, 115.77, 114.85, 94.50, 91.60,68.26, 68.19, 53.53, 34.74, 31.82, 31.76, 31.41, 29.46, 29.36, 25.90,25.88, 22.79, 22.76, 14.22, 14.19.

Synthesis of Tetra-Cyclization Trimer 706b:

To a solution of 704b (50 mg, 0.058 mmol) in 20 mL of anhydrous CH₂Cl₂was added 0.1 mL of triflic acid at −40° C. After 1 hour, TLC indicatedthe reaction was complete. The solution was quenched with saturatedNaHCO₃ solution (2.0 mL), and then washed with H₂O (2×10 mL). Thesolvent was dried (Na₂SO₄) and removed under reduced pressure. Theresidue was purified by column chromatography (First: SiO₂, hexane/DCM,75/25, v/v; Second: neutral Al₂O₃, toluene) to give thetetra-cyclization trimer 706b (21 mg, 43%) as orange solids. ¹H NMR (400MHz, CDCl₃) δ 8.23 (s, 2H), 7.79 (s, 2H), 6.51-6.91 (br, 8H), 3.85 (s,6H), 1.62 (s, 9H). ¹³C NMR (126 MHz, CDCl₃) δ 158.48, 149.59, 139.83,136.74, 131.57, 128.23, 126.11, 124.06, 122.89, 120.46, 55.60, 35.36,32.06. HRMS (ESI, positive) m/z calcd for C₆₂H₅₄O₄ [M]⁺ 862.4022, found862.3993 (see FIGS. 23A and 23B for NMR spectra).

One-Step Synthesis of Tetra-Cyclization Trimer 706:

In a flame dried flask under a nitrogen atmosphere, 702 (0.08 mmol) wasdissolved in anhydrous DCM (50 mL), and cooled to 0° C. Methanesulfonicacid (5 drops) was added by syring to the solution. After 1 hour, thereaction was cooled down to −40° C., then 0.1 mL of triflic acid wasadded and the reaction was allowed to continue for additional 1 hour.The solution was quenched with saturated NaHCO₃ solution (2.0 mL), andthen washed with H₂O (2×20 mL). The solvent was dried (Na₂SO₄) andremoved under reduced pressure. The residue was purified by columnchromatography (First: SiO₂, hexane/DCM; Second: neutral Al₂O₃,hexane/toluene,) to give the tetra-cyclization trimer 706.

706a (41 mg, 38%). ¹H NMR (400 MHz, CDCl₃) δ 8.22 (s, 4H), 7.79 (s, 4H),6.76 (d, J=148.2 Hz, 16H), 3.99 (m, 8H), 2.01-1.71 (m, 8H), 1.70-0.92(m, 74H), 0.89 (d, J=6.8 Hz, 12H). ¹³C NMR (101 MHz, cdcl₃) δ 157.99,149.51, 139.93, 136.56, 131.59, 128.12, 126.09, 124.10, 122.78, 120.43,68.35, 35.35, 32.08, 32.06, 29.86, 29.81, 29.78, 29.68, 29.57, 29.52,26.28, 22.86, 14.29. HRMS (ESI, positive) m/z calcd for C₉H₁₁₀O₄ [M]⁺1254.8404, found 1254.8389 (see FIGS. 22A and 22B for NMR spectra).

706c (45 mg, 45%). ¹H NMR (500 MHz, CDCl₃) δ 8.23 (s, 2H), 7.79 (s, 2H),6.46-6.94 (br, 8H), 3.92-3.85 (m, 4H), 1.83-1.78 (m, 2H), 1.63 (s, 9H),1.52-1.35 (m, 16H), 1.02-0.94 (m, 12H). ¹³C NMR (126 MHz, CDCl₃) δ158.28, 149.49, 139.96, 136.52, 131.59, 128.17, 126.12, 124.11, 122.77,120.44, 70.96, 70.94, 39.59, 39.55, 35.35, 32.07, 30.75, 29.86, 29.33,24.08, 23.31, 23.28, 14.33, 14.32, 11.32, 11.31. HRMS (ESI, positive)m/z calcd for C₉H₁₁₀O₄ [M]⁺ 1254.8404, found 1254.8389 (see FIGS. 24Aand 24B for NMR spectra).

706d (49 mg, 49%)¹H NMR (400 MHz, cdcl₃) δ 8.23 (s, 4H), 7.80 (s, 4H),6.85 (br, 16H), 4.12-3.87 (m, 8H), 1.97-1.74 (m, 8H), 1.74-1.19 (m,42H), 1.05-0.85 (m, 12H). ¹³C NMR (100 MHz, cdcl₃) δ 157.99, 149.51,139.93, 136.56, 131.59, 128.12, 126.09, 124.10, 122.79, 120.43, 68.34,35.34, 32.06, 31.86, 29.53, 25.95, 22.83, 14.26 (see FIG. 51 for NMRspectrum).

Synthesis of Compound 104b:

To the solution of biphenyl-2,2′-ditrifluoromethanesulfonate (2.25 g, 5mmol, 1.0 equiv.) and the terminal alkyne (2.54 g, 11 mmol, 2.2 equiv.)in Et₃N (30 mL) and DMF (50 mL), were added Pd(PPh₃)₂Cl₂ (35 mg, 0.05mmol) and CuI (19 mg, 0.1 mmol). The resulting mixture refluxed under N₂atmosphere overnight. The solvent was removed under reduced pressure andthe residue was purified by column chromatography (SiO₂, hexane/DCM) toafford the corresponding compound 104b (2.38 g, 78%) as yellow oil. ¹HNMR (500 MHz, CDCl₃) δ 7.68 (d, J=7.2 Hz, 2H), 7.59 (d, J=7.7 Hz, 2H),7.52 (t, J=7.4 Hz, 2H), 7.47 (d, J=7.3 Hz, 1H), 7.31 (t, J=7.7 Hz, 1H),7.17 (d, J=8.7 Hz, 4H), 6.82 (d, J=8.7 Hz, 4H), 3.84 (d, J=5.4 Hz, 4H),1.77-1.71 (m, 2H), 1.59-1.28 (m, 17H), 0.96 (m, 12H). ¹³C NMR (126 MHz,CDCl₃) δ 159.53, 145.88, 139.47, 132.89, 131.50, 130.57, 127.52, 127.41,127.11, 123.65, 115.16, 114.55, 93.26, 87.73, 70.63, 39.42, 30.61,29.18, 23.95, 23.16, 14.21, 11.21. HRMS (ESI, positive) m/z calcd forC₄₄H₅₀O₂ [M]⁺ 610.3811, found 610.3814.

Synthesis of Compound 106b:

In a 250 mL flame-dried flask, compound 104b (61 mg, 0.1 mmol) wasdissolved in 150 mL of anhydrous CH₂Cl₂. Trifluoroacetic acid (0.1 mL,1.3 mmol) was added and the reaction stirred under nitrogen. Afterstirring for 1 h at room temperature, the reaction was quenched withsaturated NaHCO₃ solution (5.0 mL), washed with H₂O (2×30 mL) and dried(Na₂SO₄). After removal of the solvent under reduced pressure, theresidue was purified by column chromatography (SiO₂, hexane/DCM) toafford the corresponding compound 106b (60 mg, 98%) as yellow oil. ¹HNMR (500 MHz, CDCl₃) δ 10.54 (d, J=8.5 Hz, 1H), 8.03 (d, J=8.0 Hz, 1H),8.00-7.96 (m, 1H), 7.87 (d, J=7.3 Hz, 1H), 7.73 (t, J=7.3 Hz, 1H),7.69-7.64 (m, 3H), 7.60 (m, 2H), 7.50 (d, J=8.5 Hz, 2H), 7.09 (d, J=8.5Hz, 2H), 7.00 (d, J=8.7 Hz, 2H), 4.01-3.90 (m, 4H), 1.87-1.77 (m, 2H),1.64-1.36 (m, 16H), 1.11-0.88 (m, 12H). ¹³C NMR (126 MHz, CDCl₃) δ159.69, 158.96, 139.10, 134.40, 132.79, 132.75, 132.63, 132.36, 131.24,131.02, 129.30, 129.25, 127.92, 126.70, 126.52, 125.78, 125.58, 119.53,115.59, 114.81, 114.39, 95.23, 91.11, 70.66, 70.61, 39.50, 39.39, 30.64,30.56, 29.18, 29.13, 23.97, 23.90, 23.14, 23.10, 14.17, 14.14, 11.22,11.17. HRMS (ESI, positive) m/z calcd for C₄₄H₅₀O₂ [M]⁺ 610.3811, found610.3807.

Synthesis of Compound 108b:

Using MSA: In a 250 mL flame-dried flask, compound 104b (61 mg, 0.1mmol) was dissolved in 150 mL of anhydrous CH₂Cl₂. Methanesulfonic acid(0.065 mL, 1.0 mmol) was added drop wise at 0° C. under nitrogen andthen the reaction warmed to room temperature. After stirring for 3 h atroom temperature, the reaction was quenched with saturated NaHCO₃solution (5.0 mL), washed with H₂O (2×30 mL) and dried (Na₂SO₄). Afterremoval of the solvent under reduced pressure, the residue was purifiedby column chromatography (SiO₂, hexane/DCM) to afford the correspondingcompound 108b (52 mg, 85%) as yellow oil.

Procedure c:

Using TFA-TfOH: In a 250 mL flame-dried flask, compound 104b (61 mg, 0.1mmol) was dissolved in 150 mL of anhydrous CH₂Cl₂. Trifluoroacetic acid(0.1 mL, 1.3 mmol) was added and the reaction stirred under nitrogen.After stirring for 1 h at room temperature (TLC showed no 104bresidual), the reaction was cool down to −40° C., 5 drops of triflicacid was added into the reaction mixture. The color changed to dark blueimmediately. The reaction was quenched with saturated NaHCO₃ solution(5.0 mL) while TLC showed no intermediate compound residual and thesolution was allowed to warm to room temperature slowly, then washedwith H₂O (2×30 mL) and dried (Na₂SO₄). After removal of the solventunder reduced pressure, the residue was purified by columnchromatography (SiO₂, hexane/DCM) to afford the corresponding compound108b (55 mg, 90%) as yellow oil. ¹H NMR (500 MHz, CDCl₃) δ 8.29 (d,J=7.9 Hz, 2H), 8.20 (d, J=7.6 Hz, 2H), 8.07-8.03 (m, 3H), 7.92 (t, J=7.9Hz, 1H), 7.62 (d, J=8.6 Hz, 4H), 7.14 (d, J=8.6 Hz, 4H), 4.03-3.97 (m,4H), 1.85 (m, 2H), 1.62-1.40 (m, 16H), 1.01 (m, 12H). ¹³C NMR (126 MHz,CDCl₃) δ 159.14, 139.58, 133.20, 131.28, 131.13, 130.95, 127.72, 126.41,125.57, 124.86, 124.24, 123.73, 114.59, 70.77, 39.65, 30.78, 29.32,24.11, 23.27, 14.30, 11.35. HRMS (ESI, positive) m/z calcd for C₄₄H₅₀O₂[M]⁺ 610.3811, found 610.3803.

Synthesis of Compound 1602:

A solution of 4-bromo-2,6-diiodoaniline (1600, 4.24 g, 10.0 mmol) in20.0 mL of 6 M HCl was cooled in an ice bath while a solution of NaNO₂(0.83 g, 12.0 mmol) in 5 mL of cold water was added dropwise. After theresulting solution of the diazonium salt was stirred at 0° C. for 30min, this solution was added dropwise to a solution of diethylamine(1.83 g, 25.0 mmol) and K₂CO₃ (6.9 g, 50.0 mmol) in 1:2 CH₃CN/water (30mL). The reaction mixture was then stirred at 0° C. for 30 min and wasextracted with CH₂Cl₂ (2×50 mL). The organic layer was then washed withbrine, dried over Na₂SO₄, filtered, and concentrated by evaporation. Thecrude product was purified by column chromatography (SiO₂, hexane/DCM)to give the pure product 1602 (3.3 g, 65% yield) as brown oil. ¹H NMR(400 MHz, CDCl₃) δ 7.97 (s, 2H), 3.76 (q, J=7.2 Hz, 4H), 1.36-1.29 (m,6H). ¹³C NMR (101 MHz, CDCl₃) δ 151.60, 141.20, 118.33, 91.72, 49.44,42.15, 15.23, 11.68. HRMS (TOFMS) calcd for C₁₀H₁₂BrI₂N₃ [M]⁺ 506.8304,found 506.8297 (see FIGS. 29A and 29B for NMR spectra).

Synthesis of Compound 1604: To the solution of compound 1602 (2.54 g, 5mmol, 1.0 equiv.) and the terminal alkyne H—CC-Ph-4-OiBu (2.54 g, 11mmol, 2.2 equiv.) in Et₃N (30 mL) and THF (60 mL), were addedPd(PPh₃)₂Cl₂ (35 mg, 0.05 mmol) and CuI (19 mg, 0.1 mmol). The resultingmixture was stirred under a N₂ atmosphere at room temperature overnight.The ammonium salt was then removed by filtration. The solvent wasremoved under reduced pressure and the residue was purified by columnchromatography (SiO₂, hexane/DCM) to afford the corresponding product1604 (3.2 g, 90%) as brown oil. ¹H NMR (500 MHz, CDCl₃) δ 7.58 (s, 2H),7.38-7.35 (m, 4H), 6.86-6.84 (m, 4H), 3.86-3.80 (m, 8H), 1.72 (m, 2H),1.47 (m, 9H), 1.36-1.28 (m, 16H), 0.94-0.91 (m, 9H). ¹³C NMR (126 MHz,CDCl₃) δ 159.62, 152.81, 135.11, 133.01, 118.80, 116.38, 115.37, 114.66,93.68, 85.65, 70.73, 39.49, 30.65, 29.22, 23.99, 23.18, 14.22, 11.25.HRMS (TOFMS) calcd for C₄₂H₅₄BrN₃O₂ [M]⁺ 711.3399, found 711.3393 (seeFIGS. 30A and 30B for NMR spectra).

Synthesis of Compound 1606: Triazene 1604 (1.43 g, 2.0 mmol) wasdissolved in iodomethane (20.0 mL) and the solution was heated in asealed heavy-walled tube at 130° C. for 24 h. The reaction mixture wascooled, and the solvent was evaporated to dryness. The residue was thendissolved in CH₂Cl₂ and the solution was filtered through a short plugof silica gel. After evaporation, the crude product was purified bycolumn chromatography (SiO₂, hexane/DCM) to afford the iodide 1606 (1.26g, 85%) as yellow oil. ¹H NMR (500 MHz, CDCl₃) δ 7.55 (d, J=8.8 Hz, 2H),7.53 (s, 1H), 6.91 (d, J=8.9 Hz, 2H), 3.91-3.85 (m, 2H), 1.75 (m, 1H),1.58-1.42 (m, 4H), 1.35 (m, 4H), 0.98-0.91 (m, 6H). ¹³C NMR (126 MHz,CDCl₃) δ 160.22, 133.32, 133.27, 132.99, 121.40, 114.77, 114.26, 105.81,95.00, 89.94, 70.71, 39.44, 30.63, 29.21, 23.97, 23.18, 14.24, 11.26.HRMS (TOFMS) calcd for C₃₈H₄₄BrIO₂ [M]⁺ 738.1569, found 738.1561 (SeeFIGS. 31A and 31B for NMR spectra).

Synthesis of Compound 1608: To a solution of aryl iodide 1606 (1.11 g,1.5 mmol, 1.0 equiv.) in THF (20 mL) at −78° C. was added a solution ofn-butyllithium in hexanes (0.6 mL, 1.5 mmol, 2.5 M, 1.0 equiv.). Afterstirring for 30 min at −78° C., trimethyl borate (0.16 g, 1.5 mmol, 1.0equiv.) was added; the reaction removed from the cooling bath andallowed to warm. Upon reaching room temperature the reaction wasquenched by the addition of 2 N HCl, then extracted with DCM. Theextract was washed with water, dried with Na₂SO₄, filtered andconcentrated in vacuo. The crude residue was purified by columnchromatography (SiO₂, hexane/DCM) to afford the aryl boronic acid 1608(0.76 g, 77%) as yellow oil. ¹H NMR (500 MHz, CDCl₃) δ 7.67 (s, 1H),7.47 (d, J=8.7 Hz, 2H), 6.89 (d, J=8.7 Hz, 2H), 6.56 (s, 1H), 3.87 (dd,J=5.7, 1.7 Hz, 2H), 1.74 (dd, J=12.2, 6.1 Hz, 1H), 1.53-1.41 (m, 4H),1.33 (m, 4H), 0.96-0.91 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 160.55,135.10, 133.42, 129.77, 124.10, 114.96, 113.14, 95.89, 87.00, 77.41,77.16, 76.90, 70.81, 39.45, 30.63, 29.21, 23.97, 23.18, 14.22, 11.25.MALDI-TOF calcd for C₃₈H₄₆BBrO₄ [M+K+H]⁺ 696.2, found 696.7 (see FIGS.32A and 32B for NMR spectra).

Synthesis of Compound 1610: The aryl boronic acid 1608 (0.66 g, 1.0mmol) and pinacol (0.14 g, 1.2 mmol) were dissolved in toluene (20.0 mL)and the solution was heated at 120° C. for 2 h. The solvent wasevaporated to dryness and the residue was purified by flash columnchromatography (SiO₂, hexane/DCM) to afford the monomer 1610 (0.69 g,94%) as yellow oil that solidified upon standing. ¹H NMR (400 MHz,CDCl₃) δ 7.56 (s, 1H), 7.43 (d, J=8.9 Hz, 2H), 6.85 (d, J=8.9 Hz, 2H),3.81 (d, J=5.8 Hz, 2H), 1.73-1.67 (m, 1H), 1.45 (m, 4H), 1.36 (s, 6H),1.31 (m, 4H), 0.91 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 159.74, 159.73,133.59, 133.01, 133.00, 128.88, 128.86, 122.72, 114.63, 114.62, 114.57,114.56, 92.06, 86.83, 84.40, 84.39, 70.51, 70.50, 39.36, 39.35, 30.53,29.12, 29.11, 24.99, 23.88, 23.07, 14.12, 11.17, 11.16. MALDI-TOF calcdfor C₄₄H₅₆BBrO₄ [M]⁺ 738.3, found 738.7 (see FIGS. 33A and 33B for NMRspectra).

Synthesis of polymer 1704c: To a degassed solution of monomer 700c (100mg, 0.135 mmol), K₂CO₃ (2 M/H2O, 1.5 mL, 3 mmol) and Aliquat® 336 (1drop) in toluene (8 mL) in a Schlenk tube, Pd(PPh₃)₄ (4.5 mg, 0.004mmol) was added quickly. The mixture was stirred at 120° C. for 3 days.Then, a degassed solution of bromobenzene (16 mg, 0.1 mmol) in toluene(0.5 mL) was added into the reaction mixture via a syringe and thereaction was refluxed for another 12 hours. The solution was cooled toroom temperature and precipitated into cold methanol (200 mL). Theresulting solid was collected by filtration and purified by columnchromatography (SiO₂, hexane/DCM) to afford the desired polymer 1704c(70 mg, 70%) as orange solid. ¹H NMR (500 MHz, CDCl₃) δ 8.32 (br, 1H),7.48 (br, 2H), 6.83 (br, 2H), 3.79 (br, 2H), 1.69 (br, 1H), 1.35 (br,8H), 0.90 (br, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 159.71, 141.77, 138.47,134.75, 133.30, 133.22, 122.73, 115.24, 114.74, 114.63, 94.14, 88.06,70.67, 39.44, 30.60, 29.18, 23.93, 23.16, 14.20, 11.22 (see FIGS. 34Aand 34B for NMR spectra).

Synthesis of nanostructures 1706c: In a 250 mL flame-dried flask,polymer 1704c (50.0 mg) was dissolved in 200 mL of anhydrous CH₂Cl₂. Tothe degassed solution was added trifluoroacetic acid (0.5 mL). Afterstirring at room temperature for 24 h, the reaction was cool down to−40° C., and then 5 drops of triflic acid was added. The reaction wasquenched with saturated NaHCO₃ solution (5.0 mL) after 1 h and thesolution was warmed to room temperature, washed with H₂O (2×10 mL) anddried (Na₂SO₄). After removal of the solvent under reduced pressure, theresidue was re-dissolved in CH₂Cl₂ (1.0 mL) and precipitated into coldmethanol (200 mL). The resulting solid was collected by filtrationwashed with methanol and dried in vacuum to give nanostructures 1706c asa black solid (47 mg, 94%). ¹H NMR (500 MHz, CDCl₃) δ 8.42-5.75 (br,5H), 4.39-3.13 (br, 2H), 2.56-0.24 (br, 11H). ¹³C NMR (126 MHz, CDCl₃) δ159.69, 159.13, 133.27, 130.32, 114.89, 107.77, 77.41, 77.16, 76.91,70.81, 39.63, 34.18, 31.60, 30.76, 29.86, 29.37, 28.88, 28.14, 28.00,26.04, 24.99, 24.07, 23.27, 14.30, 11.36.

By comparing the ¹H-NMR spectra (FIG. 41) for 104b, 106b and 108b (seeabove for structures), the signal located around 10.5 ppm should beattributed to the proton pointing to the alkyne in the mono-cyclizedproduct, and the signal disappeared in the bis-cyclized product (pyrenederivative). So, the appearance and disappearance of this signal can bea strong evidence of the efficiency of the alkyne benzannulation. Basedon this, a small scale reaction was performed in the NMR tube, usingdeuterated trifluoroacetic acid (TFA-d) as Lewis acid to promote thereaction. First, a NMR tube was charged with polymer 8 (2 mg, 0.004 mmol(based on repeat unit molecular weight)) and CDCl₃ (0.6 mL). Aftercomplete dissolution, the first NMR test of just polymer was taken. Thesecond NMR test was run immediately after TFA-d (15 μl, 0.2 mmol) wasadded, and the next NMR tests were run one by one after certain time torecord the reaction (FIG. 42). The results showed that some new signalsappeared and strengthened increasingly in the region of 10.5˜11.3 ppmafter addition of TFA-d, which indicated the formation of mono-cyclizedproducts; as time goes on, these signals weakened gradually but still alittle residual even after 12 hours. The other parallel reaction withmore TFA (100 equiv.) was run at the same time and quenched after 12hours. The NMR of GNR-TFA showed trace signals around 10.5-11.0 ppm,which mean the vast majority of alkynes participated in the cyclizationreaction (FIG. 43). Comparing the ¹H NMR of polymer and GNR, all thepeaks were relatively sharp before cyclization, which is due to theflexibility of the polymer (FIG. 44). After cyclization, because of therigidity of GNRs, the peaks became broad and weak, which also indicatedthe happening of cyclization.

FIG. 45 provides partial IR spectra of polymer (blue) and polymerpromoted by TFA (red), MSA (light blue) and TFA-TfOH (green),separately. The yellow oval shape marked the infrared absorption peak ofalkyne. The polymer exhibited strong absorption of alkyne in this area(blue), while the polymer promoted by TFA and MSA showed weak absorption(red and light blue). The polymer promoted by TFA-TfOH did not show anyabsorption of alkyne in this area, which indicated that no alkyneresidue in this nanoribbon, confirming that TFA-TfOH promoted fullcyclization of alkynes.

As shown in FIG. 46, due to the intramolecular H . . . H repulsionbetween the phenyl groups at the backbone of the molecules results in asignificant tilt of the latter with respect to the surface. The lineprofiles referring to the GNR (lower part of corresponding STM images)show that the distance between two phenyl groups on the same side isaround 1.25 nm before calibration. Using atomic resolution STM image ofHOPG as standard, it was found that the distance between two carbonatoms was 0.27 nm on HOPG, which is greater than the theoretical value(0.25 nm). According to this, the distance between two phenyl groups onthe same side is around 1.16 nm after calibration, which is correspondedclosely to the longitudinal length of three repeating units (around 0.9nm). The internal alkyl chains on the edge of the GNR could be alsoobserved (FIG. 47).

Synthesis of Compound C: To a solution of terminal alkyne compound B(1.85 g, 7.2 mmol) in THF (50 mL) at −78° C. under nitrogen atmospherewas added a hexane solution of n-BuLi (2.5 M, 2.8 mL, 7 mmol). Afterbeing stirred at −78° C. for 30 min and then at 0° C. for 15 min, to theresulting solution at 0° C. was added compound A (1.0 g, 2.4 mmol).After being stirred at room temperature for 16 h, the reaction mixturewas quenched with saturated NH₄Cl and then extracted with CH₂Cl₂. Theorganic layer was washed with H₂O and brine and dried over Na₂SO₄. Afterevaporation of solvents, the residue was dissolved in CH₃CN (100 mL).SnCl₂ (1.3 g, 7 mmol) and 2 mL of water was added and the reactionrefluxed for 12 hrs. After evaporation of solvents, the residue waspurified by column chromatography (SiO₂, hexane/DCM) to afford thecompound C (1.62 g, 75%). ¹H NMR (500 MHz, CDCl₃) δ 7.55-7.47 (m, 6H),7.43-7.39 (m, 4H), 7.01 (d, J=8.4 Hz, 4H), 6.75 (d, J=8.4 Hz, 4H), 3.92(t, J=6.6 Hz, 4H), 1.79-1.73 (m, 4H), 1.45-1.28 (m, 28H), 0.90 (t, J=6.9Hz, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 159.80, 145.53, 141.10, 133.22,129.67, 128.20, 128.05, 126.71, 125.13, 114.56, 100.63, 87.62, 68.21,32.04, 29.70, 29.69, 29.51, 29.46, 29.28, 26.13, 22.83, 14.27.

Synthesis of compound D: To a mixture of B (155 mg, 0.6 mmol), C (180mg, 0.2 mmol), PdCl₂(PPh₃)₂ (14.3 mg, 0.02 mmol), CuI (7.6 mg, 0.04mmol), and PPh₃ (10.4 mg, 0.04 mmol) under nitrogen atmosphere was addedEt₃N (30 mL). The resulting mixture was stirred at refluxing temperaturefor 24 h. After evaporation of Et3N, the residue was purified by columnchromatography (SiO₂, hexane/DCM) to afford the compound D (130 mg,52%). ¹H NMR (500 MHz, CDCl₃) δ 7.65 (d, J=7.1 Hz, 4H), 7.54-7.44 (m,6H), 7.13 (d, J=8.7 Hz, 8H), 6.76 (d, J=8.7 Hz, 8H), 3.93 (t, J=6.6 Hz,8H), 1.79-1.73 (m, 8H), 1.45-1.26 (m, 56H), 0.88 (t, J=6.8 Hz, 12H). ¹³CNMR (101 MHz, CDCl₃) δ 159.49, 145.31, 139.51, 133.06, 130.50, 127.75,127.60, 124.90, 115.43, 114.60, 98.70, 87.47, 68.22, 32.05, 29.72,29.70, 29.53, 29.47, 29.32, 26.16, 22.84, 14.27.

1-Bromo-4-tert-butylbenzene (213 mg, 1 mmol), 2,6-diynylphenyl borate (1mmol) and K₂CO₃ (276 mg, 2 mmol) were dissolved in THF (60 mL) and water(10 mL) solution. Pd(PPh₃)₄ (58 mg, 0.05 mmol) was added to the solutionbefore degassing the mixture via bubbling nitrogen for 30 min. Theresulting mixture was stirred under a N₂ atmosphere at 80° C. for 24 h.After the reaction was complete, the mixture was diluted with DCM,washed with H₂O and dried over Na₂SO₄. The solvent was removed underreduced pressure and the residue was purified by column chromatographyto give compound 902.

902a: 86% yield. ¹H NMR (500 MHz, cdcl₃) δ 7.59 (s, 2H), 7.55 (d, J=8.3Hz, 2H), 7.50 (d, J=8.3 Hz, 2H), 7.13 (d, J=8.7 Hz, 4H), 6.78 (d, J=8.7Hz, 4H), 3.79 (s, 6H), 1.44 (s, 9H), 1.40 (s, 9H). ¹³C NMR (125 MHz,cdcl₃) δ 159.59, 150.07, 149.92, 143.60, 136.56, 133.24, 132.95, 130.31,128.71, 124.28, 123.18, 115.75, 114.17, 113.93, 92.40, 88.72, 55.40,34.81, 34.68, 31.65, 31.33.

902b: ¹H NMR (400 MHz, cdcl₃) δ 7.60 (s, 2H), 7.57 (d, J=8.4 Hz, 2H),7.52 (d, J=8.4 Hz, 2H), 7.13 (d, J=8.7 Hz, 4H), 6.78 (d, J=8.8 Hz, 4H),3.94 (t, J=6.5 Hz, 4H), 1.81-1.75 (m, 4H), 1.45 (s, 9H), 1.42 (s, 9H),1.36 (m, 12H), 0.93 (t, J=6.1 Hz, 6H). ¹³C NMR (100 MHz, cdcl₃) δ159.19, 150.02, 149.87, 143.58, 136.59, 132.92, 130.32, 128.63, 124.26,123.22, 115.47, 114.45, 92.53, 88.64, 68.15, 34.80, 34.67, 31.71, 31.65,31.32, 29.30, 25.83, 22.74, 14.17.

902c: ¹H NMR (400 MHz, cdcl3) δ 7.61 (s, 2H), 7.58 (d, J=8.6 Hz, 2H),7.53 (d, J=8.6 Hz, 2H), 7.14 (d, J=8.9 Hz, 4H), 6.79 (d, J=8.9 Hz, 4H),3.94 (t, J=6.6 Hz, 4H), 1.82-1.75 (m, 4H), 1.39 (dd, J=47.3, 14.7 Hz,46H), 0.93 (t, J=6.9 Hz, 6H). ¹³C NMR (100 MHz, cdcl₃) δ 159.16, 149.98,149.84, 143.57, 136.58, 132.90, 130.33, 128.60, 124.25, 123.22, 115.45,114.42, 92.53, 88.63, 68.11, 34.78, 34.65, 32.05, 31.65, 31.31, 29.72,29.70, 29.53, 29.47, 29.33, 26.15, 22.84, 14.28.

902′: In a 100 mL flame-dried flask, compound 900 (53 mg, 0.1 mmol) wasdissolved in 50 mL of anhydrous CH₂Cl₂. Trifluoroacetic acid (570 mg, 5mmol) was added and the reaction stirred under nitrogen. After stirringfor 1 h at room temperature (TLC showed no residual 900), the reactionwas quenched with saturated NaHCO₃ solution (5 mL). The solution wasthen washed with H₂O (2×30 mL) and dried (Na₂SO₄). After removal of thesolvent under reduced pressure, the residue was purified by columnchromatography (SiO₂, DCM) to afford the compound 902′ (52 mg, 99%) asyellow solid. ¹H NMR (400 MHz, cdcl₃) δ 10.37 (d, J=9.0 Hz, 1H), 8.00(d, J=2.2 Hz, 1H), 7.98 (d, J=2.2 Hz, 1H), 7.83 (d, J=2.2 Hz, 1H), 7.75(dd, J=9.0, 2.2 Hz, 1H), 7.70-7.67 (m, 2H), 7.64 (s, 1H), 7.53-7.49 (m,2H), 7.10-7.05 (m, 2H), 7.02-6.98 (m, 2H), 3.93 (s, 3H), 3.89 (s, 3H),1.48 (s, 9H), 1.38 (s, 9H). ¹³C NMR (126 MHz, cdcl₃) δ 159.86, 159.07,149.10, 148.20, 139.17, 133.44, 133.23, 132.99, 132.73, 132.62, 132.01,131.27, 131.17, 129.09, 128.41, 127.20, 126.12, 125.80, 123.81, 122.63,118.91, 116.25, 114.36, 114.16, 113.95, 113.83, 94.24, 91.84, 55.51,55.48, 35.03, 34.67, 31.47, 31.43.

904a: In a 200 mL flame-dried flask, the 902′ (52 mg, 0.1 mmol) wasdissolved in 100 mL of anhydrous CH₂Cl₂. 1 drop of triflic acid wasadded into the reaction mixture at 0° C., and the color of the solutionchanged to dark blue immediately. After stirring for 15 min at 0° C.,the reaction was quenched with saturated NaHCO₃ solution (5 mL). Thesolution was then washed with H₂O (2×30 mL) and dried (Na₂SO₄). Afterremoval of the solvent under reduced pressure, the residue was purifiedby column chromatography (SiO₂, hexane/DCM 3:1) to afford the compound904a (27 mg, 52%) as yellow solid. Single crystal was obtained byrecrystallizing from a chloroform and methanol solution of 904a via slowevaporation at room temperature. ¹H NMR (500 MHz, cdcl₃) δ 8.30 (s, 2H),8.19 (s, 2H), 7.98 (s, 2H), 7.64 (d, J=8.7 Hz, 4H), 7.13 (d, J=8.7 Hz,4H), 3.96 (s, 6H), 1.59 (s, 9H), 1.39 (s, 9H). ¹³C NMR (100 MHz, cdcl₃)δ 159.15, 149.16, 148.06, 139.44, 133.84, 131.28, 130.58, 130.54,127.91, 123.71, 121.95, 121.24, 113.95, 55.53, 35.60, 35.36, 32.09,31.95.

One-step synthesis of Compound 904: In a 100 mL flame-dried flask,compound 900 (0.1 mmol) was dissolved in 50 mL of anhydrous CH₂Cl₂.Trifluoroacetic acid (570 mg, 5 mmol) was added and the reaction stirredunder nitrogen. After stirring for 1 h at room temperature (TLC showedno residual 1), the reaction was cool down to 0° C., then 1 drop oftriflic acid was added. After stirring for 15 min at 0° C., the reactionwas quenched with saturated NaHCO₃ solution (5 mL). The solution wasthen washed with H₂O (2×30 mL) and dried (Na₂SO₄). After removal of thesolvent under reduced pressure, the residue was purified by columnchromatography (SiO₂, hexane/DCM 3:1) to afford the compound 904.

904b: ¹H NMR (400 MHz, cdcl₃) δ 8.34 (s, 2H), 8.21 (s, 2H), 8.01 (s,2H), 7.65 (d, J=8.6 Hz, 4H), 7.13 (d, J=8.7 Hz, 4H), 4.12 (t, J=6.6 Hz,4H), 1.94-1.86 (m, 4H), 1.61 (s, 9H), 1.58-1.40 (m, 21H), 1.00-0.94 (m,6H). ¹³C NMR (100 MHz, cdcl₃) δ 158.73, 149.11, 148.02, 139.53, 133.63,131.24, 130.61, 130.55, 127.87, 123.73, 121.96, 121.90, 121.27, 114.51,68.29, 35.60, 35.35, 32.09, 31.96, 31.84, 29.55, 26.00, 22.82, 14.24.

904c: ¹H NMR (400 MHz, cdcl₃) δ 8.32 (s, 2H), 8.19 (s, 2H), 7.99 (s,2H), 7.63 (d, J=8.7 Hz, 4H), 7.12 (d, J=8.8 Hz, 4H), 4.11 (t, J=6.6 Hz,4H), 1.96-1.81 (m, 4H), 1.59 (s, 9H), 1.53-1.09 (m, 37H), 0.92 (t, J=6.8Hz, 6H). ¹³C NMR (101 MHz, cdcl₃) δ 158.73, 149.11, 148.02, 139.52,133.63, 131.24, 130.61, 130.55, 129.53, 127.87, 123.72, 121.90, 121.27,114.51, 68.31, 35.60, 35.35, 32.09, 31.96, 29.80, 29.77, 29.65, 29.60,29.52, 26.33, 22.87, 14.30.

Compound 1000 was prepared as described for compound 900, using compound1000′ and 2-bromopyrene as starting material.

1000a: ¹H NMR (400 MHz, cdcl₃) δ 8.54 (s, 2H), 8.27 (s, 2H), 8.12 (m,4H), 7.73 (s, 2H), 7.00 (d, J=8.9 Hz, 4H), 6.62 (d, J=9.0 Hz, 4H), 3.69(s, 6H), 1.64 (s, 9H), 1.48 (s, 9H). ¹³C NMR (100 MHz, cdcl₃) δ 159.53,150.36, 149.13, 142.82, 136.39, 132.88, 131.40, 130.29, 129.42, 127.78,127.58, 127.53, 124.11, 123.59, 123.21, 122.17, 115.35, 113.92, 92.40,88.64, 55.28, 35.43, 34.78, 32.14, 31.36.

1000b: ¹H NMR (400 MHz, cdcl₃) δ 8.59 (s, 2H), 8.30 (s, 2H), 8.14 (m,4H), 7.77 (s, 2H), 7.02 (d, J=8.9 Hz, 4H), 6.63 (d, J=8.9 Hz, 4H), 3.83(t, J=6.6 Hz, 4H), 1.83-1.59 (m, 13H), 1.54-1.44 (m, 9H), 1.35 (m, 12H),0.91 (t, J=6.9 Hz, 6H). ¹³C NMR (100 MHz, cdcl₃) δ 159.13, 150.32,149.09, 142.77, 136.41, 132.84, 131.39, 130.28, 129.35, 127.79, 127.61,127.51, 124.10, 123.64, 123.21, 122.15, 115.06, 114.43, 92.55, 88.57,68.02, 35.40, 34.76, 32.13, 31.65, 31.36, 29.20, 25.75, 22.69, 14.14.

1000c: ¹H NMR (400 MHz, cdcl₃) δ 8.61 (s, 2H), 8.14 (m, 7H), 7.75 (s,2H), 7.00 (d, J=8.7 Hz, 4H), 6.62 (d, J=8.7 Hz, 4H), 3.82 (t, J=6.5 Hz,4H), 1.74-1.63 (m, 4H), 1.53-1.25 (m, 37H), 0.91 (t, J=6.9 Hz, 6H). ¹³CNMR (100 MHz, cdcl₃) δ 159.17, 150.41, 142.61, 136.80, 132.85, 131.56,130.48, 129.40, 127.90, 127.80, 127.33, 125.93, 124.98, 124.90, 124.16,123.65, 115.04, 114.44, 92.59, 88.52, 68.05, 34.77, 32.03, 31.75, 31.36,29.67, 29.48, 29.45, 29.25, 26.08, 22.82, 14.26.

1002a: ¹H NMR (400 MHz, cdcl₃) δ 11.17 (s, 1H), 8.25 (d, J=1.7 Hz, 1H),8.23-8.16 (m, 4H), 8.08 (d, J=9.0 Hz, 1H), 8.03 (d, J=2.2 Hz, 1H), 7.90(s, 1H), 7.80 (m, 3H), 7.46 (d, J=8.7 Hz, 2H), 7.08-7.03 (m, 4H), 3.95(s, 3H), 3.91 (s, 3H), 1.64 (s, 9H), 1.60 (s, 9H). ¹³C NMR (100 MHz,cdcl₃) δ 159.92, 158.93, 149.36, 148.96, 138.55, 138.15, 133.02, 132.84,132.45, 131.63, 131.06, 130.61, 130.20, 129.77, 128.89, 128.50, 128.12,128.07, 127.64, 127.21, 126.39, 125.41, 124.72, 124.46, 123.55, 122.99,122.43, 121.90, 119.74, 116.12, 114.43, 114.42, 94.46, 92.07, 55.45,55.44, 35.29, 34.78, 32.01, 31.46.

1002c: FTIR (neat) cm⁻¹. ¹H NMR (400 MHz, cdcl₃) δ 11.13 (s, 1H), 8.17(dd, J=9.2, 4.5 Hz, 2H), 8.11 (q, J=6.7 Hz, 3H), 8.03 (d, J=9.0 Hz, 1H),7.99-7.95 (m, 2H), 7.84 (s, 1H), 7.74 (dd, J=11.5, 9.1 Hz, 3H), 7.39 (d,J=8.7 Hz, 2H), 7.01 (dd, J=8.7, 1.7 Hz, 4H), 4.06 (m, 4H), 1.89-1.82 (m,4H), 1.53 (s, 12H), 1.40-1.26 (m, 25H), 0.90 (t, J=6.8 Hz, 6H). ¹³C NMR(100 MHz, cdcl₃) δ 159.61, 158.57, 149.14, 138.66, 137.97, 133.04,132.90, 132.51, 131.82, 131.25, 130.80, 130.18, 129.98, 128.98, 128.69,128.18, 127.82, 127.57, 127.53, 126.50, 126.22, 125.40, 125.09, 124.82,124.73, 124.55, 124.54, 123.76, 119.83, 115.84, 115.09, 115.01, 94.64,91.88, 68.34, 34.82, 32.09, 32.07, 31.48, 29.86, 29.79, 29.76, 29.74,29.65, 29.59, 29.56, 29.52, 29.50, 29.42, 26.30, 26.23, 22.86, 14.29.

1004a: ¹H NMR (400 MHz, cdcl₃) δ 8.34 (s, 2H), 8.25 (d, J=9.4 Hz, 2H),8.21 (s, 4H), 7.77 (d, J=9.5 Hz, 2H), 7.48 (d, J=8.6 Hz, 4H), 7.05 (d,J=8.7 Hz, 4H), 3.95 (s, 6H), 1.64 (s, 9H), 1.59 (s, 9H). ¹³C NMR (100MHz, cdcl₃) δ 158.92, 149.75, 149.27, 139.29, 138.71, 133.07, 131.14,131.01, 130.83, 130.29, 128.28, 125.97, 125.56, 124.83, 124.63, 124.43,122.60, 122.47, 121.70, 114.51, 55.56, 35.35, 35.30, 32.05, 31.48.

1004b: ¹H NMR (400 MHz, cdcl₃) δ 8.35 (s, 2H), 8.28 (d, J=9.4 Hz, 2H),8.22 (d, J=1.1 Hz, 4H), 7.78 (d, J=9.5 Hz, 2H), 7.46 (d, J=8.7 Hz, 4H),7.04 (d, J=8.7 Hz, 4H), 4.10 (t, J=6.6 Hz, 4H), 1.89 (m, 4H), 1.65 (s,9H), 1.60 (s, 9H), 1.57-1.32 (m, 12H), 0.98 (t, J=7.1 Hz, 6H). ¹³C NMR(100 MHz, cdcl₃) δ 158.49, 149.71, 149.23, 139.38, 138.50, 131.10,131.03, 130.84, 130.25, 128.33, 125.99, 125.57, 124.86, 124.59, 124.42,122.69, 122.55, 122.43, 121.68, 115.11, 68.32, 35.34, 35.29, 32.05,31.86, 29.55, 25.99, 22.82, 14.26.

1004c: ¹H NMR (400 MHz, cdcl₃) δ 8.34 (s, 2H), 8.30 (d, J=9.4 Hz, 2H),8.21 (s, 2H), 8.16 (d, J=7.6 Hz, 2H), 8.01 (dd, J=8.0, 7.1 Hz, 1H), 7.77(d, J=9.5 Hz, 2H), 7.45 (d, J=8.7 Hz, 4H), 7.03 (d, J=8.7 Hz, 4H), 4.09(t, J=6.6 Hz, 4H), 1.94-1.84 (m, 4H), 1.63 (s, 9H), 1.55-1.26 (m, 28H),0.91 (t, J=6.9 Hz, 6H). ¹³C NMR (101 MHz, cdcl₃) δ 158.51, 149.85,139.38, 138.46, 131.23, 131.04, 130.98, 130.24, 128.36, 126.13, 126.08,125.67, 125.15, 124.93, 124.53, 124.46, 124.34, 122.64, 121.58, 115.14,68.35, 35.37, 32.09, 32.05, 29.80, 29.77, 29.67, 29.58, 29.52, 26.31,22.87, 14.30.

Compound 1100: 2,7-dibromopyrene (360 mg, 1 mmol), 2,6-diynylphenylborate (2.5 mmol) and K₂CO₃ (552 mg, 4 mmol) were dissolved in toluene(80 mL) and water (20 mL) solution. Pd(PPh₃)₄ (116 mg, 0.1 mmol) wasadded to the solution before degassing the mixture via bubbling nitrogenfor 30 min. The resulting mixture was stirred under a N₂ atmosphere at80° C. for 48 h. After the reaction was complete, the mixture wasdiluted with DCM, washed with H₂O and dried over Na₂SO₄. The solvent wasremoved under reduced pressure and the residue was purified by columnchromatography to give compound 1100.

1100a: ¹H NMR (400 MHz, cdcl₃) δ 8.63 (s, 4H), 8.20 (s, 4H), 7.76 (s,4H), 7.03 (d, J=8.9 Hz, 8H), 6.61 (d, J=8.9 Hz, 8H), 3.76 (t, J=6.6 Hz,8H), 1.67 (m, 8H), 1.50 (s, 18H), 1.39-1.23 (m, 24H), 0.87 (t, J=6.9 Hz,12H). ¹³C NMR (100 MHz, cdcl₃) δ 159.21, 150.39, 142.62, 136.69, 132.86,130.74, 129.42, 127.72, 127.64, 124.33, 123.65, 114.98, 114.51, 92.69,88.63, 68.02, 34.79, 31.65, 31.37, 29.19, 25.72, 22.68, 14.13.

1100b: ¹H NMR (400 MHz, cdcl₃) δ 8.60 (s, 4H), 8.17 (s, 4H), 7.73 (s,4H), 7.00 (d, J=8.9 Hz, 8H), 6.58 (d, J=9.0 Hz, 8H), 3.74 (t, J=6.6 Hz,8H), 1.69-1.58 (m, 8H), 1.51 (s, 18H), 1.41-1.09 (m, 56H), 0.87 (t,J=6.9 Hz, 12H). ¹³C NMR (101 MHz, cdcl₃) δ 159.22, 150.39, 142.62,136.69, 132.87, 130.74, 129.42, 127.72, 127.64, 124.33, 123.65, 114.99,114.52, 92.69, 88.63, 68.05, 34.80, 32.03, 31.38, 29.68, 29.67, 29.49,29.45, 29.25, 26.07, 22.82, 14.26.

In a 100 mL flame-dried flask, compound 1100b (0.1 mmol) was dissolvedin 80 mL of anhydrous CH₂Cl₂. Trifluoroacetic acid (570 mg, 5 mmol) wasadded and the reaction stirred under nitrogen. After stirring for 1 h atroom temperature, the reaction was quenched with saturated NaHCO₃solution (15 mL). The solution was then washed with H₂O (2×50 mL) anddried (Na₂SO₄). After removal of the solvent under reduced pressure, theresidue was purified by column chromatography (SiO₂, DCM) to afford themixture of compound 1102b and 1104b (148 mg, 99%) as yellow oil. ¹H NMR(500 MHz, cdcl₃) δ 11.03 (s, 1H), 11.00 (s, 2H), 8.21 (d, J=9.4 Hz, 1H),8.13 (s, 2H), 8.09 (d, J=2.1 Hz, 2H), 8.06 (d, J=2.1 Hz, 1H), 7.95-7.92(m, 3H), 7.89 (s, 2H), 7.79 (d, J=5.6 Hz, 3H), 7.71-7.68 (m, 3H),7.61-7.57 (m, 2H), 7.43 (d, J=8.7 Hz, 2H), 7.38-7.33 (m, 3H), 7.03-6.89(m, 11H), 4.07 (t, J=6.6 Hz, 5H), 4.00-3.94 (m, 5H), 1.93-1.75 (m, 13H),1.56-1.26 (m, 110H), 0.95-0.88 (m, 24H). ¹³C NMR (101 MHz, cdcl₃) δ159.58, 159.55, 158.59, 158.51, 149.11, 148.99, 138.72, 137.93, 137.48,133.05, 133.00, 132.84, 132.68, 132.53, 131.22, 131.01, 130.24, 130.21,130.14, 129.46, 128.98, 128.58, 128.47, 127.97, 127.38, 127.32, 126.34,126.27, 125.67, 125.34, 124.57, 124.51, 123.60, 119.90, 119.78, 115.86,115.74, 114.99, 114.95, 94.57, 94.52, 91.87, 91.75, 68.33, 34.81, 32.10,32.08, 31.49, 31.47, 29.85, 29.81, 29.77, 29.75, 29.68, 29.65, 29.61,29.58, 29.54, 29.51, 29.44, 26.34, 26.31, 26.24, 26.23, 22.86, 14.29(see FIG. 53 for an X-ray image of compound 1102b).

In a 100 mL flame-dried flask, compound 1100 (0.1 mmol) was dissolved in80 mL of anhydrous CH₂Cl₂. Trifluoroacetic acid (570 mg, 5 mmol) wasadded and the reaction stirred under nitrogen for 1 h at roomtemperature. The solution was slowly added into the precooled triflicacid (2 equiv.) of CH₂Cl₂ (50 mL) solution at 0° C. After stirring for30 min at 0° C., the reaction was quenched with saturated NaHCO₃solution (20 mL), washed with H₂O (2×50 mL) and dried (Na₂SO₄). Afterremoval of the solvent under reduced pressure, the residue was purifiedby column chromatography to afford the compound 1106 as deep red solid.

1106a: ¹H NMR (400 MHz, cdcl₃) δ 8.30 (s, 4H), 8.14 (s, 4H), 8.10 (s,4H), 7.41 (d, J=8.7 Hz, 8H), 6.95 (d, J=8.8 Hz, 8H), 4.05 (t, J=6.6 Hz,8H), 1.91-1.79 (m, 8H), 1.62 (s, 18H), 1.56-1.48 (m, 8H), 1.39 (m, 16H),0.94 (t, J=7.1 Hz, 12H). ¹³C NMR (100 MHz, cdcl₃) δ 158.38, 149.75,139.35, 138.19, 131.36, 131.19, 130.07, 126.05, 125.73, 125.46, 124.75,124.51, 122.52, 121.47, 115.09, 68.28, 35.36, 32.05, 31.86, 29.56,25.97, 22.82, 14.24.

1106b: ¹H NMR (400 MHz, toluene) δ 8.59 (s, 4H), 8.25 (s, 4H), 8.12 (s,4H), 7.27 (d, J=8.6 Hz, 8H), 6.82 (d, J=8.7 Hz, 8H), 3.67 (t, J=6.5 Hz,8H), 1.74-1.48 (m, 26H), 1.43-1.18 (m, 56H), 0.92 (t, J=6.8 Hz, 12H).¹³C NMR (100 MHz, toluene) δ 159.01, 149.75, 140.10, 138.60, 132.09,131.90, 130.55, 126.95, 126.49, 126.27, 125.95, 125.40, 122.94, 122.36,115.34, 68.05, 53.40, 35.45, 32.58, 32.18, 30.35, 30.31, 30.21, 30.07,30.05, 26.74, 23.34, 14.54 (see FIG. 54).

¹H NMR (400 MHz, cdcl₃) δ 7.50 (s, 2H), 7.19 (d, J=3.6 Hz, 2H), 6.71(dt, J=3.5, 0.8 Hz, 2H), 2.82 (t, J=7.6 Hz, 4H), 1.70 (dt, J=15.2, 7.4Hz, 4H), 1.54-1.17 (m, 21H), 1.01-0.83 (m, 6H). ¹³C NMR (100 MHz, cdcl₃)δ 150.19, 149.22, 132.65, 129.85, 125.89, 124.60, 124.46, 120.09, 91.59,87.46, 34.66, 31.66, 31.64, 31.09, 30.39, 28.84, 22.70, 14.21.

¹H NMR (400 MHz, cdcl₃) δ 7.49 (s, 2H), 7.10 (d, J=3.6 Hz, 2H), 6.67 (d,J=3.6 Hz, 2H), 2.80 (t, J=7.5 Hz, 4H), 1.74-1.64 (m, 4H), 1.57-1.17 (m,33H), 0.91 (t, J=6.9 Hz, 6H). ¹³C NMR (100 MHz, cdcl₃) δ 152.29, 148.21,131.88, 128.75, 126.55, 124.19, 120.86, 93.05, 84.36, 83.89, 34.71,31.61, 31.55, 31.03, 30.28, 28.76, 25.14, 22.65, 14.15.

¹H NMR (400 MHz, cdcl₃) δ 8.51 (s, 2H), 8.27 (s, 2H), 8.13 (m, 4H), 7.71(s, 2H), 6.66 (d, J=3.6 Hz, 2H), 6.46 (d, J=3.6 Hz, 2H), 2.64 (t, J=7.6Hz, 4H), 1.64 (s, 9H), 1.36 (d, J=83.2 Hz, 34H), 0.88 (t, J=6.8 Hz, 6H).¹³C NMR (100 MHz, cdcl3) δ 150.37, 149.04, 148.49, 142.51, 135.87,131.87, 131.42, 130.37, 129.34, 127.97, 127.41, 127.35, 124.20, 124.15,123.33, 123.16, 122.08, 120.41, 92.87, 86.35, 35.40, 34.79, 32.14,31.61, 31.48, 31.32, 30.23, 28.74, 22.65, 14.19.

¹H NMR (400 MHz, cdcl₃) δ 8.57 (d, J=9.4 Hz, 2H), 8.43 (s, 2H), 8.40 (s,2H), 8.32 (s, 2H), 7.94 (d, J=9.4 Hz, 2H), 7.06 (d, J=3.4 Hz, 2H), 6.91(d, J=3.4 Hz, 2H), 2.98 (t, J=7.4 Hz, 4H), 1.83 (m, 4H), 1.75-1.59 (m,18H), 1.57-1.40 (m, 12H), 1.02 (t, J=6.9 Hz, 6H). ¹³C NMR (100 MHz,cdcl₃) δ 149.81, 149.27, 146.50, 145.17, 132.39, 131.90, 130.98, 130.75,127.65, 126.17, 125.85, 125.25, 125.01, 124.89, 124.65, 124.49, 123.07,122.62, 122.58, 122.39, 35.33, 35.30, 32.07, 32.01, 31.97, 31.87, 30.46,28.89, 22.88, 14.37.

¹H NMR (400 MHz, cdcl₃) δ 8.54 (s, 4H), 8.18 (s, 4H), 7.70 (s, 4H), 6.67(d, J=3.6 Hz, 4H), 6.43 (d, J=3.6 Hz, 4H), 2.59 (t, J=7.5 Hz, 8H), 1.46(s, 18H), 1.24 (m, 32H), 0.87-0.80 (m, 12H). ¹³C NMR (100 MHz, cdcl₃) δ150.39, 148.57, 142.42, 136.12, 131.95, 130.84, 129.37, 127.78, 127.33,124.36, 124.17, 124.15, 123.35, 120.39, 92.93, 86.47, 34.81, 31.62,31.49, 31.34, 30.24, 28.79, 22.67, 14.17.

¹H NMR (400 MHz, cdcl₃) δ 8.35 (s, 4H), 8.33 (s, 4H), 8.31 (s, 4H), 6.90(d, J=3.4 Hz, 4H), 6.81 (d, J=3.4 Hz, 4H), 2.94 (t, J=7.6 Hz, 8H),1.81-1.75 (m, 8H), 1.64-1.61 (m, 18H), 1.50-1.37 (m, 24H), 0.91 (m,12H). ¹³C NMR (100 MHz, cdcl₃) δ 149.95, 145.93, 144.68, 132.51, 132.00,130.84, 126.21, 126.01, 125.50, 124.99, 124.87, 124.74, 124.45, 123.04,122.09, 35.37, 32.01, 32.00, 31.83, 30.59, 29.06, 22.82, 14.30 (see FIG.52).

In view of the many possible embodiments to which the principles of thepresent disclosure may be applied, it should be recognized that theillustrated embodiments are only preferred examples of the disclosureand should not be taken as limiting the scope of the claimed invention.Rather, the scope of is defined by the following claims. We thereforeclaim as our invention all that comes within the scope and spirit ofthese claims.

1. A compound having a structure satisfying Formula 1

wherein each R¹ independently is a heteroaliphatic substituent; eachR^(a) independently is an aryl group substituted with one or morefunctional groups selected from aliphatic, alkoxy, amide, amine,thioether, haloalkyl, nitro, halo, or silyl; or an electron-donatinggroup; each n independently is 1, 2, or 3; and m is an integer rangingfrom 2 to
 200. 2. The compound of claim 1, wherein each R^(a)independently is:

or an electron-donating group.
 3. The compound of claim 1, wherein theelectron-donating group is an alkoxy group.
 4. The compound of claim 1,wherein each R¹ independently is a heteroaliphatic group including atleast one sulfur atom.
 5. The compound of claim 4, wherein theheteroaliphatic group including at least one sulfur atom is a thioether.6. The compound of claim 4, wherein the heteroaliphatic group includingat least one sulfur atom is a thiol.
 7. The compound of claim 1, havinga structure:

wherein: each R¹ is independently a heteroaliphatic moiety; each R^(a)independently is an electron-donating group or an aryl group substitutedwith one or more functional groups selected from aliphatic, alkoxy,amide, amine, thioether, haloalkyl, nitro, or halo; and m is an integerranging from 2 to
 200. 8. The compound of claim 7, wherein each R^(a)independently is an aryl group substituted with one or more functionalgroups selected from aliphatic, amine, or nitro.
 9. The compound ofclaim 7, wherein each R^(a) independently is:

or an electron-donating group.
 10. The compound of claim 9, wherein theelectron-donating group is an alkoxy group.
 11. The compound of claim 7,wherein each R¹ independently is heteroaliphatic group including atleast one sulfur atom.
 12. The compound of claim 11, wherein theheteroaliphatic group including at least one sulfur atom is a thioether.13. The compound of claim 11, wherein the heteroaliphatic groupincluding at least one sulfur atom is a thiol.
 14. A compound, having astructure:

wherein: each R¹ is independently a heteroaliphatic moiety selected froma thiol, a thioether, or a disulfide; each R^(a) independently isselected from an ether, a -(poly)ethylene glycol, or an aryl groupsubstituted with one or more functional groups selected from aliphatic,amine, or nitro; and m is an integer ranging from 2 to
 200. 15. Thecompound of claim 14, wherein the disulfide is —CH₂SSH, —CH₂CH₂SSH, or—SCH₂CH₂SSH.
 16. The compound of claim 14, wherein the thiol is —CH₂SH,—CH₂CH₂SH, or —SCH₂CH₂SH.
 17. The compound of claim 14, wherein thethioether is —SCH₃, —CH₂SCH₃, —CH₂CH₂SCH₃, or —SCH₂CH₂SCH₃.